CN102712186A - Multilayer blow-molded container, and process for production thereof - Google Patents
Multilayer blow-molded container, and process for production thereof Download PDFInfo
- Publication number
- CN102712186A CN102712186A CN2011800062784A CN201180006278A CN102712186A CN 102712186 A CN102712186 A CN 102712186A CN 2011800062784 A CN2011800062784 A CN 2011800062784A CN 201180006278 A CN201180006278 A CN 201180006278A CN 102712186 A CN102712186 A CN 102712186A
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- Prior art keywords
- alpha
- ethene
- olefin
- olefin copolymer
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- Prior art date
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- 238000000034 method Methods 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 230000008569 process Effects 0.000 title description 2
- 239000004711 α-olefin Substances 0.000 claims abstract description 208
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 205
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 204
- 239000000203 mixture Substances 0.000 claims abstract description 179
- 229920005989 resin Polymers 0.000 claims abstract description 169
- 239000011347 resin Substances 0.000 claims abstract description 169
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 153
- 229920000098 polyolefin Polymers 0.000 claims abstract description 125
- 238000002844 melting Methods 0.000 claims abstract description 103
- 230000008018 melting Effects 0.000 claims abstract description 103
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229920001577 copolymer Polymers 0.000 claims abstract description 42
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 146
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 claims description 60
- 229920000642 polymer Polymers 0.000 claims description 52
- 238000006116 polymerization reaction Methods 0.000 claims description 50
- -1 aromatic phosphonic acid ester compound Chemical class 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- 238000000071 blow moulding Methods 0.000 claims description 35
- 238000000465 moulding Methods 0.000 claims description 27
- 150000001336 alkenes Chemical class 0.000 claims description 22
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 claims description 20
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- 238000010103 injection stretch blow moulding Methods 0.000 claims description 9
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- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
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- 206010009866 Cold sweat Diseases 0.000 description 40
- 239000000463 material Substances 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 239000000155 melt Substances 0.000 description 31
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- 238000012360 testing method Methods 0.000 description 23
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- 239000003054 catalyst Substances 0.000 description 21
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
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- 239000012968 metallocene catalyst Substances 0.000 description 12
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- 239000004700 high-density polyethylene Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
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- 239000003795 chemical substances by application Substances 0.000 description 9
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- 229920001684 low density polyethylene Polymers 0.000 description 9
- 239000004702 low-density polyethylene Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 9
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 8
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 238000012797 qualification Methods 0.000 description 8
- 229920006132 styrene block copolymer Polymers 0.000 description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 6
- 241000790917 Dioxys <bee> Species 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 208000035389 Ring chromosome 6 syndrome Diseases 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 238000005422 blasting Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
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- 238000010792 warming Methods 0.000 description 5
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
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- 150000001993 dienes Chemical class 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
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- OEANSHQKEMMQQJ-UHFFFAOYSA-N C=CCCCCCCC.CC1=C(C(=O)O)C=CC=C1C(=O)O Chemical compound C=CCCCCCCC.CC1=C(C(=O)O)C=CC=C1C(=O)O OEANSHQKEMMQQJ-UHFFFAOYSA-N 0.000 description 3
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- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
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Abstract
Disclosed is a multilayer blow-molded container having high gloss, excellent surface appearance and excellent impact resistance. The multilayer blow-molded container is characterized in that a resin to be used for the outermost layer comprises an olefin polymer composition (E) comprising a propylene resin (A), an ethylene-alpha-olefin copolymer (B) and a nucleating agent (D), the propylene resin (A) comprises a copolymer of propylene and an alpha-olefin (A-1) and has a crystal melting point of 140 to 155 DEG C (A-2), the ethylene-alpha-olefin copolymer (B) comprises a copolymer of ethylene and at least one alpha-olefin having 4 to 20 carbon atoms (B-1) and has a crystal melting point of not lower than 85 DEG C and lower than 110 DEG C (B-2), and the olefin polymer composition (E) has an MFR value of 5 to 10 g/10 min (E-1).
Description
Technical field
The present invention relates to multilayered blow container and manufacturing approach thereof.
Background technology
As the raw material of blow molded articles such as blow-molded container, for example can use resins such as vinyl chloride resin, polycarbonate resin, vinyl resins, propylene resin according to purposes.
Among these resins, when using the vinyl resins of the such hard of high density polyethylene (HDPE), the problem of glossy variation when using the such soft vinyl resins of low density polyethylene (LDPE), has the low problem of rigidity.
In addition, when using vinyl chloride resin, though excellent on the gloss, environmental problem is arranged, when using polycarbonate resin, though very excellent on the gloss, problems such as manufacturing cost rising are arranged.
On the other hand, when using propylene resin, resulting blow molded article, more excellent than high density polyethylene (HDPE) on gloss, the transparency because manufacturing cost is cheap relatively, therefore extensive container as liquid lotion, cosmetics, food, medicine etc. uses.
The gloss of blow molded article is the rerum natura that all the time is studied in order to tackle the market demands that need good appearance, but does not propose to satisfy simultaneously the blow molded article of sufficient gloss, good mouldability and resistance to impact as yet.
As the excellent blow molded article of gloss; A kind of multi-layer blow molding body has been proposed; Wherein, as substrate resin, the LLDPE that with crystalline melting point is 110～125 ℃ is as cooperating resin with propylene-alpha-olefin copolymers; The olefin polymer compositions that will contain these resins and nucleator is as outermost layer (for example, with reference to patent documentation 1).Yet inventor of the present invention discovers that even the multi-layer blow molding body of record in the patent documentation 1, gloss and resistance to impact are also still insufficient, also needs further to improve.
As the excellent multilayer bottle of resistance to cold, the sandwich layer of barrier properties for gases resin, the multilayer bottle (for example, with reference to patent documentation 2) that outermost layer is formed by polyolefin resin and straight chain shape ultra-low density polyethylene resin have been proposed to have.Yet inventor of the present invention discovers that even the multilayer bottle of record in the patent documentation 2, gloss and mouldability are also still insufficient, also needs further to improve.
As having excellent gloss, prima facie multilayer plastic container of making by (In-mold) mode in the mould that has label; The container (for example, with reference to patent documentation 3) that comprises the polypropylene random copolymer resin that contains the ethene composition, polyvinyl resin, nucleator, ethene-alpha-olefin copolymer resin is used in proposition as the used resin of outermost layer.Yet inventor of the present invention discovers, the multilayer plastic container of record in the patent documentation 3, and resistance to impact is still insufficient, needs further to improve.
As the excellent high glaze blow-molded container of the gloss of container outer surface; Known outermost layer uses the composition of the ethene-alpha-olefin copolymer that comprises that the polypropylene-based resin that uses metallocene catalyst and obtain obtains with using metallocene catalyst; High glaze blow-molded container (for example, with reference to patent documentation 4) through the moulding of multi-layer blow molding method.Yet inventor of the present invention discovers that the high glaze blow-molded container of record though compare the gloss excellence with existing container, has further room for improvement at aspects such as hear resistance, gloss in the patent documentation 4.
The prior art document
Patent documentation
Patent documentation 1: No. 3106834 communique of Japan Patent
Patent documentation 2: japanese kokai publication hei 6-72424 communique
Patent documentation 3: japanese kokai publication hei 7-304123 communique
Patent documentation 4: TOHKEMY 2003-137928 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide the also excellent multilayered blow container of equilibrium of a kind of high glaze, appearance excellence and resistance to impact excellence and resistance to impact and anti-being clamminess property.
Be used to solve the method for problem
Inventor of the present invention has carried out deep repeatedly research in order to accomplish above-mentioned problem; The result finds, the multilayered blow container that outermost layer uses specific olefin polymer compositions to obtain, high glaze; Appearance is excellent; And resistance to impact is excellent, and the equilibrium of resistance to impact and anti-being clamminess property is also excellent, thereby has accomplished the present invention.
Promptly; Multilayered blow container of the present invention is characterised in that; The employed resin of outermost layer comprises olefin polymer compositions (E); This olefin polymer compositions (E) contains propylene resin (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions (wherein, (A) with (B) 100 weight portions that add up to) and nucleator (D) 0.01～0.5 weight portion, and aforesaid propylene resinoid (A) satisfies following condition (A-1) and (A-2); Above-mentioned ethene-alpha-olefin copolymer (B) satisfies following condition (B-1) and (B-2), and above-mentioned olefin polymer compositions (E) satisfies following condition (E-1).
(A-1) for propylene be selected from the copolymer that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin.
(A-2) according to JIS-K7121, the crystalline melting point that records with differential scanning calorimetry (DSC) (DSC) is 140～155 ℃ a scope.
(B-1) for ethene and the carbon number more than a kind be the copolymer of 4～20 alpha-olefin.
(B-2) according to JIS-K7121, the crystalline melting point that records with DSC is more than 85 ℃ and less than 110 ℃ scope.
(E-1), be 5～10g/10 minute scope to measure melt flow rate (MFR) (MFR) that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.
Viewpoint from the low temperature resistance to impact of multilayered blow container; Preferred above-mentioned polymerization of olefines compositions (E) also contains low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion; Above-mentioned low density ethylene-alpha olefin copolymer (F) satisfies following condition (F-1) and (F-2), the density (d that above-mentioned ethene-alpha-olefin copolymer (B) records with the density gradient column method
B[g/cm
3]) and the density (d that records with the density gradient column method of low density ethylene-alpha olefin copolymer (F)
F[g/cm
3]) satisfy following condition (X-1).
(F-1) for ethene and the carbon number more than a kind be the copolymer of 3～20 alpha-olefin.
(F-2) according to JIS-K7121, the crystalline melting point that records with DSC is below 89 ℃, or does not observe the peak based on crystalline melting point.
（X－1）d
B[g/cm
3]＞d
F[g/cm
3]，0.010[g/cm
3]≤（d
B－d
F）[g/cm
3]≤0.050[g/cm
3]。
Preferred above-mentioned ethene-alpha-olefin copolymer (B) also satisfies following condition (B-4).
(B-4) density that records with the density gradient column method is 0.880～0.910g/cm
3Scope.
From the viewpoint of the low temperature resistance to impact of multilayered blow container, preferred above-mentioned ethene-alpha-olefin copolymer (B) also satisfies following condition (B-4a), and above-mentioned low density ethylene-alpha olefin copolymer (F) also satisfies following condition (F-3).
(B-4a) density (d that records with the density gradient column method
B[g/cm
3]) be 0.890～0.910g/cm
3Scope.
(F-3) density (d that records with the density gradient column method
F[g/cm
3]) be 0.865～0.900g/cm
3Scope.
Preferred aforesaid propylene resinoid (A) also satisfies following condition (A-4).
(A-4) Mw/Mn that records through GPC is more than 4.0.
Preferred aforesaid propylene resinoid (A) also satisfies following condition (A-3).
(A-3), be 5～10g/10 minute scope to measure MFR that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.
Preferred above-mentioned ethene-alpha-olefin copolymer (B) also satisfies following condition (B-5).
(B-5) Mw/Mn that records through GPC is 1.2～3.0.
Preferred above-mentioned ethene-alpha-olefin copolymer (B) also satisfies following condition (B-3).
(B-3), be 5～10g/10 minute scope to measure MFR that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.
Preferred above-mentioned nucleator (D) is for being selected from the compound more than a kind in aromatic phosphonic acid ester compound, carboxylic metallic salt nucleator, polymer nucleator, sorbose alcohols nucleator and the inorganic compound nucleator.
Preferred aforesaid propylene resinoid (A) is 95.5～98 weight portions, and above-mentioned ethene-alpha-olefin copolymer (B) is 2～4.5 weight portions (wherein, (A) with (B) 100 weight portions that add up to).
Like each described multilayered blow container in the claim 1～10, it is characterized in that above-mentioned multilayered blow container has at least one internal layer, this internal layer is formed by acronal (G) or polyvinyls (H).
Preferred above-mentioned multilayered blow container obtains through direct blow molding method or the moulding of injection stretch blow molding method.
Multilayered blow container of the present invention is characterised in that; Use above-mentioned olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin composition in addition; Form outermost layer with above-mentioned olefin polymer compositions (E); Above-mentioned olefin polymer compositions (E) thermoplastic resin composition in addition forms the mode of at least one internal layer, through direct blow molding method or the moulding of injection stretch blow molding method.
The effect of invention
According to the present invention, the also excellent multilayered blow container of equilibrium of high glaze, appearance excellence and resistance to impact excellence and resistance to impact and anti-being clamminess property can be provided.
The specific embodiment
Then, the present invention is described particularly.
[multilayered blow container]
Multilayered blow container of the present invention is characterised in that the employed resin of outermost layer comprises olefin polymer compositions (E), and this olefin polymer compositions (E) contains propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D).
Multilayered blow container of the present invention, high glaze, appearance is excellent, and resistance to impact is excellent, also contains in the mode of low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion at olefin polymer compositions (E), and the low temperature resistance to impact is also excellent.
＜propylene resin (A)＞
The propylene resin that uses among the present invention (A) satisfies following condition (A-1) and (A-2), preferably further satisfies at least one among following condition (A-3), (A-4), more preferably satisfies following condition (A-3) and (A-4).Propylene resin (A) can use a kind of separately, also can use two or more.
(A-1) for propylene be selected from the copolymer that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin.Wherein, It as carbon number 4～20 alpha-olefin; Can enumerate 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-laurylene, 1-hexadecylene, 4-methyl-1-pentene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 3-methyl-1-butene, 3; 3-dimethyl-1-butylene, diethyl-1-butylene, trimethyl-1-butylene, 3-Methyl-1-pentene, ethyl-1-amylene, propyl group-1-amylene, dimethyl-1-amylene, first and second bases-1-amylene, diethyl-1-hexene, trimethyl-1-amylene, 3-methyl isophthalic acid-hexene, dimethyl-1-hexene, 3; 5,5-trimethyl-1-hexene, first and second bases-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl isophthalic acid-nonene etc.
As the propylene resin that uses among the present invention (A); Consider from the aspect of the equilibrium of rerum natura, economy; Be preferably propylene and be selected from the copolymer that ethene and carbon number are the alkene more than a kind in 4～10 the alpha-olefin; More preferably propylene be selected from the copolymer of the alpha-olefin more than a kind in ethene and the 1-butylene, be preferably the copolymer of propylene and ethene especially.
In addition, the propylene resin that uses among the present invention (A) is preferably random copolymer.
(A-2) according to JIS-K7121, the crystalline melting point that records with differential scanning calorimetry (DSC) (DSC) is 140～155 ℃ a scope.If crystalline melting point is in above-mentioned scope, then the gloss of multilayered blow container and resistance to impact are excellent, and the mouldability when making multilayered blow container is also excellent, so preferred.According to JIS-K7121, the crystalline melting point that records with differential scanning calorimetry (DSC) (DSC) is if be higher than 155 ℃, then the poor impact resistance of multilayered blow container.In addition, according to JIS-K7121, the crystalline melting point that records with differential scanning calorimetry (DSC) (DSC) is if be lower than 140 ℃, and the insufficient formability when then making multilayered blow container produces on the surface of multilayered blow container and to be clamminess.
The crystalline melting point of aforesaid propylene resinoid (A) can use differential scanning calorimetry (DSC) (DSC) (for example, PerkinElmer corporate system Diamond DSC) to measure and try to achieve with following condition determination through according to JIS-K7121.The summit of endothermic peak in the time of wherein, will measuring with following condition determination, in the 3rd step is defined as crystalline melting point (Tm).Endothermic peak has when a plurality of, and the endothermic peak summit that the height at peak is maximum is defined as crystalline melting point (Tm).
(condition determination)
Measure environment: nitrogen atmosphere
Sample size: 5mg
Sample shape: press mold (230 ℃ of moulding, thickness 200～400 μ m)
The 1st step: be warmed up to 240 ℃ from 30 ℃ with 10 ℃/min, keep 10min.
The 2nd step: cool to 60 ℃ with 10 ℃/min.
The 3rd step: be warmed up to 240 ℃ with 10 ℃/min.
The crystalline melting point that aforesaid propylene resinoid (A) records with differential scanning calorimetry (DSC) (DSC) according to JIS-K7121, for example can through in the manufacturing that changes propylene resin (A) during copolymerization be selected from ethene and the carbon number of propylene and importing be that the importing ratio of the alkene more than a kind in 4～20 the alpha-olefin is adjusted.Promptly; Through increase with respect to the import volume of propylene, be selected from the import volume that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin; Can reduce the crystalline melting point that records with differential scanning calorimetry (DSC) (DSC) according to JIS-K7121; Through reduce with respect to the import volume of propylene, be selected from the import volume that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin, can improve the crystalline melting point that records with differential scanning calorimetry (DSC) (DSC) according to JIS-K7121.
(A-3), be 5～10g/10 minute scope to measure MFR that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.Wherein, MFR is meant the meaning of melt flow rate (MFR).If MFR is in above-mentioned scope; Then the flowability of the olefin polymer compositions (E) during moulding is the scope that is suitable for moulding of the present invention; The uneven thickness of the olefin polymer compositions (E) of multilayer can be prevented in the blow molding, the also excellent multilayered blow container of flatness excellence and then gloss can be made.According to ASTM D-1238; To measure MFR that 230 ℃ of temperature, 2.16kg load record if greater than 10g/10 minute; The mouldability when then making multilayered blow container sometimes and the poor impact resistance of multilayered blow container; According to ASTM D-1238, if to measure MFR that 230 ℃ of temperature, 2.16kg load record less than 5g/10 minute, then the glossiness of multilayered blow container is poor sometimes.
Aforesaid propylene resinoid (A) is according to ASTM D-1238, to measure the MFR that 230 ℃ of temperature, 2.16kg load record, for example can by in the manufacturing of propylene resin (A) when the copolymerization import volume of employed chain-transferring agent (for example hydrogen) adjust.Promptly; The propylene that imports when increasing with respect to polymerization be selected from import volume amount, chain-transferring agent (for example hydrogen) that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin, can improve propylene resin (A) according to ASTM D-1238 to measure the MFR that 230 ℃ of temperature, 2.16kg are loaded and recorded.In addition; The propylene that imports when reducing with respect to polymerization be selected from import volume amount, chain-transferring agent (for example hydrogen) that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin, can reduce propylene resin (A) according to ASTM D-1238 to measure the MFR that 230 ℃ of temperature, 2.16kg are loaded and recorded.
In addition, in the presence of radical initiators such as organic peroxide, carry out melting mixing through the propylene resin that polymerization is obtained and handle, also can adjust the MFR that records with 230 ℃ of temperature of mensuration, 2.16kg load according to ASTM D-1238.For example, handle, according to ASTM D-1238, increase to measure the MFR that 230 ℃ of temperature, 2.16kg load record through in the presence of organic peroxide, carrying out melting mixing.In addition, through increasing the addition of organic peroxide, can further improve according to ASTM D-1238, to measure the MFR that 230 ℃ of temperature, 2.16kg load record.
(A-4) Mw/Mn that records through GPC is more than 4.0.Wherein, GPC is the meaning of gel permeation chromatography, and Mw is the meaning of weight average molecular weight, and Mn is the meaning of number-average molecular weight, and Mw/Mn is the index of molecular weight distribution.As propylene resin (A), Mw/Mn is preferably more than 1.5, more preferably more than 3.0; But if satisfy above-mentioned (A-4), that is, if Mw/Mn is more than 4.0; Then can obtain the excellent blow molded article of gloss, so preferred especially owing to do not receive the surface roughness affects of blow mold.Although its reason is still indeterminate, inventor of the present invention considers as follows.That is,, then compare, have the more part and the more low-molecular-weight part of HMW with situation less than this scope if Mw/Mn is more than 4.0.Can think resin flows distortion when the existence of the part of HMW more reduces blow molding, the existence of more low-molecular-weight part is accelerated to solidify.Therefore; Inventor of the present invention infers; If use the composition of the scope of above-mentioned Mw/Mn as (A) composition; Then no matter use the big mould of surface roughness also to be to use the little mould of surface roughness, resulting multilayered blow container can roller mould the roughness on surface, and form good gloss.In addition, do not limit as the upper limit of Mw/Mn is special, but be generally 50.0, be preferably 30.0 from the viewpoint of productivity ratio, more preferably 20.0, be more preferably 16.0, be preferably 12.0 especially, most preferably be 8.0.Wherein, measuring Mw/Mn through GPC can carry out with the method for putting down in writing among the embodiment.
The Mw/Mn that aforesaid propylene resinoid (A) records through GPC, for example, the kind of the catalyst that uses during manufacturing that can be through propylene resin (A) is adjusted.For example, can be met the propylene resin (A) of above-mentioned condition (A-4) through using Ziegler-Natta catalyst, preferably use solid titanium catalyst as catalyst.In addition, as other the example of method of adjustment Mw/Mn, the method for the different propylene resin more than 2 kinds of combined molecular weight is arranged.Particularly from the viewpoint of the part that forms above-mentioned more HMW, solid titanium catalyst is favourable.
In addition, as propylene resin (A), will by
13That C-NMR calculates, from the construction unit of propylene be that the total of the construction unit of the alkene more than a kind in 4～20 the alpha-olefin is when being made as 100 weight % from being selected from ethene and carbon number; Be generally the scope of 80～99 weight % from the weight of the construction unit of propylene, be preferably the scope of 90～99 weight %.In addition, be the scope that the weight of the construction unit of the alkene more than a kind in 4～20 the alpha-olefin is generally 1～20 weight % from being selected from ethene and carbon number, be preferably the scope of 1～10 weight %.In the time of in above-mentioned scope, the equilibrium of the rerum natura of the mouldability when making multilayered blow container and the being clamminess property of multilayered blow container etc. is good, so preferred.
Will by
13C-NMR calculate from the construction unit of propylene be the total of the construction unit of the alkene more than a kind in 4～20 the alpha-olefin when being made as 100 weight % from being selected from ethene and carbon number, measure, calculate with following condition from the weight of the construction unit of propylene.
(
13The C-NMR condition determination)
Determinator: the system LA400 of NEC type nuclear magnetic resonance device
Mode determination: BCM (Bilevel Complete decoupling)
Observing frequency: 100.4MHz
Observation scope: 17006.8Hz
45 ° of pulse width: C nuclears (7.8 μ second)
Pulse-recurrence time: 5 seconds
Coupon:
Coupon rotating speed: 12Hz
The tired number of times of calculating: 20000 times
Measure temperature: 125 ℃
Solvent: 1,2,4-trichloro-benzenes: 0.35ml/ heavy benzol: 0.2ml
Sample size: about 40mg
(from the Weight Calculation of the construction unit of propylene)
When being selected from ethene and carbon number and being the alkene more than a kind (being comonomer) in 4～20 the alpha-olefin, according to following document (1), through from resulting for ethene
13The C-NMR spectrogram is confirmed the distribute ratio of (two unit groups (2 cellular chain) distribution) of monomer chain, can calculate in the propylene resin (A) mole fraction (mol%) from the construction unit of ethene (below be designated as E (mol%)) and from the mole fraction (mol%) of the construction unit of propylene (below be designated as P (mol%)).Be scaled weight % from the E (mol%) and the P (mol%) that are obtained, can calculate in the propylene resin (A) from the weight % of the construction unit of propylene with from the weight % of the construction unit of ethene.
Document (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Macromolecules 1982,15, (4), 1150-1152
When being selected from ethene and carbon number is the alkene more than a kind (being comonomer) in 4～20 the alpha-olefin when being 4～20 alpha-olefin for carbon number, according to following document (2), through from resulting
13The C-NMR spectrogram is confirmed the monomer chain ratio of (two unit groups (2 cellular chain) distribution) that distributes, and in the propylene resin (A) is the mole fraction (mol%) (below be designated as A (mol%)) of the construction unit of 4～20 alpha-olefin and from the mole fraction (mol%) of the construction unit of propylene (below be designated as P (mol%)) from carbon number thereby can calculate.Be scaled weight % from the A (mol%) and the P (mol%) that try to achieve, can calculate in the propylene resin (A) is the weight % of the construction unit of 4～20 alpha-olefin from the weight % of the construction unit of propylene with from carbon number.
Document (2): James C.Randall, Macromolecules, 1978,11,592-597
Adjustment from the weight of the construction unit of propylene can be through the amount of stating after the adjustment arbitrarily that is made as of creating conditions.More detailed; Through in the manufacturing that reduces propylene resin (A) when the copolymerization with respect to the import volume of propylene, be selected from the import volume that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin, can increase weight from the construction unit of propylene.In addition, through increase with respect to the import volume of propylene, to be selected from from ethene and carbon number be the import volume of the alkene more than a kind in 4～20 the alpha-olefin, can reduce the weight from the construction unit of propylene.
In addition, preferred aforesaid propylene resinoid (A) for propylene be selected from the random copolymer that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin.Aforesaid propylene resinoid (A) can be through in the presence of Ziegler-Natta catalyst or metallocene catalyst, with propylene and be selected from ethene and carbon number is that the alkene more than a kind in 4～20 the alpha-olefin carries out copolymerization, preferably carries out random copolymerization and obtain.As the catalyst that uses when the polymerization aforesaid propylene resinoid (A), if use Ziegler-Natta catalyst, preferably use solid titanium catalyst, can satisfy above-mentioned condition (A-4).In addition, through the different propylene resin more than 2 kinds (A) of combined molecular weight, also can be adjusted into satisfy condition (A-4).In addition, when polymerization, also can import with hydrogen is the chain-transferring agent of representative.And, also can the propylene resin that obtained by polymerization be carried out the melting mixing processing and obtain propylene resin (A) in the presence of radical initiators such as organic peroxide.
As above-mentioned organic peroxide, though not special the qualification, can the illustration benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide acetic acid butyl ester, tert-butylperoxy isopropyl carbonate, 2; 5-dimethyl-2,5-two (benzoyl peroxide) hexane, 2,5-dimethyl-2; 5-two (benzoyl peroxide) hexin-3, the diperoxy adipic acid tert-butyl ester, peroxidating-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, cumyl peroxide, 2; 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5;-dimethyl-2,5-two (tert-butyl peroxide) hexin-3,1, two (tert-butyl peroxide isopropyl) benzene of 3-, tert-butyl hydroperoxide diisopropylbenzene (DIPB), 1; Two (tert-butyl peroxide)-3,3 of 1-, 5-trimethyl-cyclohexane, 1; Two (tert-butyl peroxide) cyclohexanes, 2 of 1-, two (tert-butyl peroxide) butane of 2-, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, hydrogen phosphide cumene, TBHP, p-Cymene hydroperoxide, 1,1; 3; 3-tetramethyl butyl hydroperoxide or 2,5-dimethyl-2, the organic peroxide of 5-two (hydrogen peroxide) hexane etc.In addition, among them, more preferably 2,5-dimethyl-2,5-two (benzoyl peroxide) hexane, 1, two (tert-butyl peroxide isopropyl) benzene of 3-.When using organic peroxide, hope to use below 0.1 weight portion with respect to the propylene resin that obtains by polymerization 100 weight portions.Melting mixing is handled the method that can be listed below: after in propylene resin, adding above-mentioned organic peroxide; Drop in the mixers such as Henschel mixer, Banbury, rotary drum mixer and mix; Then; The mixture that obtains through extruder moulding such as single screw extrusion machine, double screw extruders, is obtained the line material of propylene resin (A).Wherein, before carrying out blow molding, use comminutor etc. is processed pellet shape to above-mentioned line material usually.
＜ethene-alpha-olefin copolymer (B)＞
The ethene-alpha-olefin copolymer that uses among the present invention (B) satisfies following condition (B-1) and (B-2), preferably also satisfies at least one among following condition (B-3), (B-4), more preferably satisfies following condition (B-3) and (B-4).In addition, also preferably satisfy following condition (B-5).Ethene-alpha-olefin copolymer (B) can use a kind of separately, also can use two or more.
(B-1) for ethene and the carbon number more than a kind be the copolymer of 4～20 alpha-olefin.Wherein, It as carbon number 4～20 alpha-olefin; Can enumerate 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-laurylene, 1-hexadecylene, 4-methyl-1-pentene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 3-methyl-1-butene, 3; 3-dimethyl-1-butylene, diethyl-1-butylene, trimethyl-1-butylene, 3-Methyl-1-pentene, ethyl-1-amylene, propyl group-1-amylene, dimethyl-1-amylene, first and second bases-1-amylene, diethyl-1-hexene, trimethyl-1-amylene, 3-methyl isophthalic acid-hexene, dimethyl-1-hexene, 3; 5,5-trimethyl-1-hexene, first and second bases-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl isophthalic acid-nonene etc.
As the ethene-alpha-olefin copolymer that uses among the present invention (B); Viewpoint from the equilibrium of rerum natura and economy; Be preferably ethene and be selected from the copolymer that carbon number is the alkene more than a kind in 4～10 the alpha-olefin; More preferably ethene be selected from the copolymer of the alpha-olefin more than a kind in 1-butylene, 1-hexene and the 1-octene, be preferably the copolymer of ethene and 1-hexene especially.
(B-2) crystalline melting point that records with DSC according to JIS-K7121 is more than 85 ℃ and is lower than 110 ℃ scope.If crystalline melting point is in above-mentioned scope, then the resistance to impact of multilayered blow container, outermost layer and other layers is excellent in adhesion, so preferred.The crystalline melting point that ethene-alpha-olefin copolymer (B) records with DSC according to JIS-K7121 is more than 110 ℃ the time; Cementability and poor impact resistance, when the crystalline melting point that records with DSC according to JIS-K7121 was lower than 85 ℃, cementability was poor; And produce and to be clamminess, so not preferred.In addition, from the viewpoint of the equilibrium of resistance to impact, cementability and being clamminess property, crystalline melting point is preferably below 109 ℃, more preferably below 108 ℃, is preferably especially below 105 ℃.
The ethene-alpha-olefin copolymer that uses among the present invention (B) can be made as amount arbitrarily according to JIS-K7121 through creating conditions of adjustment ethene-alpha-olefin copolymer with the crystalline melting point that DSC records.
More specifically, in the polymerization of ethene-alpha-olefin copolymer (B), the ratio of the ethene that can be when changing polymerizing ethylene-alpha olefin copolymer and the feeding quantity of alpha-olefin is adjusted.Particularly, through the feeding quantity of increase, can reduce the crystalline melting point that records with DSC according to JIS-K7121 with respect to the alpha-olefin of the feeding quantity of ethene.In addition, through the feeding quantity of minimizing, can improve the crystalline melting point that records with DSC according to JIS-K7121 with respect to the alpha-olefin of the feeding quantity of ethene.
The crystalline melting point of above-mentioned ethene-alpha-olefin copolymer (B) can use differential scanning calorimetry (DSC) (DSC) to measure according to JIS-K7121.Particularly, can be by measuring with the same method of the crystalline melting point of above-mentioned propylene resin (A).
(B-3), be 5～10g/10 minute scope to measure MFR that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.If MFR is in above-mentioned scope, then ethene-alpha-olefin copolymer (B) is to the favorable dispersibility of propylene resin (A), and the glossiness of multilayered blow container, resistance to impact are excellent, and outermost layer and other layers excellent in adhesion is so preferably.
In addition, ethene-alpha-olefin copolymer (B) is according to ASTM D-1238, to measure the adjustment of the MFR that 230 ℃ of temperature, 2.16kg load record, can be made as value arbitrarily through adjusting creating conditions of ethene-alpha-olefin copolymer (B).
More specifically, after in the polymerization of the ethene-alpha-olefin copolymer (B) stated, can be through adjustment the feeding quantity of hydrogen of feeding quantity of ethene and/or alpha-olefin during with respect to polymerization control.The feeding quantity of the hydrogen of the feeding quantity of the ethylene gas when increasing with respect to polymerization; Perhaps when adding ethene and alpha-olefin; Increase is with respect to the feeding quantity of the hydrogen of the feeding quantity of ethene and alpha-olefin, can improve according to ASTM D-1238, to measure the MFR that 230 ℃ of temperature, 2.16kg load record.Through the feeding quantity of minimizing with respect to the hydrogen of the feeding quantity of ethylene gas; Perhaps when adding ethene and alpha-olefin; Minimizing is with respect to the feeding quantity of the hydrogen of the feeding quantity of ethene and alpha-olefin, can reduce according to ASTM D-1238, to measure the MFR that 230 ℃ of temperature, 2.16kg load record.
(B-4) density that records with the density gradient column method is 0.880～0.910g/cm
3Scope.If density is in above-mentioned scope, then the gloss of multilayered blow container and resistance to impact, outermost layer and other layers is excellent in adhesion, so preferred.
In addition, when multilayered blow container of the present invention is used to need the purposes of low temperature resistance to impact, low density ethylene-alpha olefin copolymer (F) of stating after preferred the use, and ethene-alpha-olefin copolymer (B) satisfies following condition (B-4a).
(B-4a) density (d that records with the density gradient column method
B[g/cm
3]) be 0.890～0.910g/cm
3Scope.If density is in above-mentioned scope; Then the gloss of multilayered blow container, resistance to impact, low temperature resistance to impact, outermost layer and other layers is excellent in adhesion; And being clamminess property is low, and shock-resistant characteristic such as resistance to impact, low temperature resistance to impact and patience is balanced good, so preferred.
The ethene-alpha-olefin copolymer that uses among the present invention (B) can be made as amount arbitrarily through creating conditions of adjustment ethene-alpha-olefin copolymer (B) with the density that the density gradient column method records.
More specifically, after in the polymerization of the ethene-alpha-olefin copolymer (B) stated, the ratio of the ethene that can be when changing polymerizing ethylene-alpha olefin copolymer and the feeding quantity of alpha-olefin is adjusted.Particularly, through the feeding quantity of increase, can reduce the density that records with the density gradient column method with respect to the alpha-olefin of the feeding quantity of ethene.In addition, through the feeding quantity of minimizing, can improve the density that records with the density gradient column method with respect to the alpha-olefin of the feeding quantity of ethene.
Wherein, The density that the ethene-alpha-olefin copolymer that uses among the present invention (B) records with the density gradient column method is that the line material of the ethene-alpha-olefin copolymer (B) that obtains during with the mensuration of above-mentioned MFR was 120 ℃ of heat treatments 1 hour; With 1 hour linearly slowly behind the cool to room temperature, the measured value that records with density gradient column.
(B-5) Mw/Mn that records through GPC is 1.2～3.0.Wherein, as ethene-alpha-olefin copolymer (B), more preferably Mw/Mn is 1.5～3.0.If Mw/Mn is in above-mentioned scope, then the gloss of multilayered blow container of the present invention is excellent, so preferred.
The Mw/Mn that above-mentioned ethene-alpha-olefin copolymer (B) records through GPC, the kind of the catalyst that uses during manufacturing that for example can be through ethene-alpha-olefin copolymer (B) is adjusted.For example, as catalyst,, can be met the ethene-alpha-olefin copolymer (B) of above-mentioned condition (B-5) through using metallocene catalyst.
In addition, above-mentioned ethene-alpha-olefin copolymer (B) can be through obtaining ethene, alpha-olefin copolymer, but ethene-alpha-olefin copolymer is preferably the copolymer that uses metallocene catalyst polymerisation to obtain.In addition, when polymerization, also can import with hydrogen is the chain-transferring agent of representative.
If the ethene-alpha-olefin copolymer of the ethene-alpha-olefin copolymer (B) that uses among the present invention for using metallocene catalyst polymerisation to obtain; Then compare with the ethene-alpha-olefin copolymer that the so-called Ziegler-Natta catalyst polymerization of existing use obtains; Composition is evenly distributed; Therefore with respect to the favorable dispersibility of propylene resin (A), can access the better olefin polymer compositions of gloss (E).In addition; If the ethene-alpha-olefin copolymer that uses metallocene catalyst polymerisation to obtain; Then compare with the ethene-alpha-olefin copolymer that uses the Ziegler-Natta catalyst polymerization to obtain, molecular weight distribution also narrows down, as the low molecular weight compositions minimizing of the main cause that resistance to impact is worsened.And; If the ethene-alpha-olefin copolymer that uses metallocene catalyst polymerisation to obtain; Then compare with the ethene-alpha-olefin copolymer that uses the Ziegler-Natta catalyst polymerization to obtain, the composition of copolymer distributes and also becomes evenly, also tails off as the amorphous component of the reason that is clamminess.In addition, the bonding inequality between outermost layer and other layers also tails off, also can expect to suppress through the time outward appearance worsen.
Can know from foregoing, use metallocene catalyst to carry out the ethene-alpha-olefin copolymer (B) that polymerization obtains, can access the gloss excellence, and resistance to impact be excellent, the olefin polymer compositions that being clamminess property is low (E) through utilizing.
＜low density ethylene-alpha olefin copolymer (F)＞
When multilayered blow container of the present invention needs the low temperature resistance to impact; As olefin polymer compositions (E), preferred use also contains the composition of low density ethylene-alpha olefin copolymer (F) in addition at propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D) as stated.
Above-mentioned low density ethylene-alpha olefin copolymer (F) satisfies following condition (F-1) and (F-2), preferably also satisfies following condition (F-3).Low density ethylene-alpha olefin copolymer (F) can use a kind of separately, also can use two or more.
(F-1) for ethene and the carbon number more than a kind be the copolymer of 3～20 alpha-olefin.Wherein, It as carbon number 3～20 alpha-olefin; Can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-laurylene, 1-hexadecylene, 4-methyl-1-pentene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 3-methyl-1-butene, 3; 3-dimethyl-1-butylene, diethyl-1-butylene, trimethyl-1-butylene, 3-Methyl-1-pentene, ethyl-1-amylene, propyl group-1-amylene, dimethyl-1-amylene, first and second bases-1-amylene, diethyl-1-hexene, trimethyl-1-amylene, 3-methyl isophthalic acid-hexene, dimethyl-1-hexene, 3; 5,5-trimethyl-1-hexene, first and second bases-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl isophthalic acid-nonene etc.
As above-mentioned low density ethylene-alpha olefin copolymer (F); Viewpoint from the equilibrium of rerum natura and economy; Be preferably ethene and be selected from the copolymer that carbon number is the alkene more than a kind in 3～10 the alpha-olefin, more preferably ethene and the copolymer that is selected from the alpha-olefin more than a kind in propylene, 1-butylene, 1-hexene and the 1-octene.As above-mentioned low density ethylene-alpha olefin copolymer (F); Wherein, Be preferably the copolymer of copolymer, ethene and 1-octene of copolymer, ethene and the 1-butylene of ethene and propylene; The copolymer of the copolymer of ethene and 1-butylene, ethene and 1-octene more preferably is preferably the copolymer of ethene and 1-butylene especially.
(F-2) according to JIS-K7121, the crystalline melting point that records with DSC is below 89 ℃, does not perhaps observe the peak based on crystalline melting point.When having crystalline melting point, be preferably below 75 ℃.If crystalline melting point is in above-mentioned scope, then multilayered blow container is excellent on the low temperature resistance to impact, so preferred.
The crystalline melting point of above-mentioned low density ethylene-alpha olefin copolymer (F) can use differential scanning calorimetry (DSC) (DSC) to measure according to JIS-K7121.Particularly, the method that embodiment put down in writing that can state is later on measured.
(F-3) density (d that records with the density gradient column method
F[g/cm
3]) be 0.865～0.900g/cm
3Scope.Above-mentioned density is 0.870～0.900g/cm more preferably
3Scope.If density is in above-mentioned scope, then the gloss of multilayered blow container is excellent, and the low temperature resistance to impact is excellent especially, so preferred.
In addition, the density (d that records with the density gradient column method of above-mentioned ethene-alpha-olefin copolymer (B)
B[g/cm
3]) and the density (d that records with the density gradient column method of low density ethylene-alpha olefin copolymer (F)
F[g/cm
3]) satisfy following condition (X-1).
（X-1）d
B[g/cm
3]＞d
F[g/cm
3]，0.010[g/cm
3]≤（d
B-d
F）[g/cm
3]≤0.050[g/cm
3]。That is, the density of low density ethylene-alpha olefin copolymer (F) is less than the density of above-mentioned ethene-alpha-olefin copolymer (B), the density contrast (d of ethene-alpha-olefin copolymer (B) and low density ethylene-alpha olefin copolymer (F)
B-d
F) be 0.010～0.050 [g/cm
3].In addition, density contrast (d
B-d
F) be preferably 0.010～0.040 [g/cm
3].
If density contrast (d
B-d
F) in above-mentioned scope, then the gloss of multilayered blow container is excellent, and the low temperature resistance to impact is excellent, so preferred.
In addition; As low density ethylene-alpha olefin copolymer (F); Preferably according to ASTM D-1238, be 0.1～50g/10 minute scope to measure MFR that 230 ℃ of temperature, 2.16kg load record; More preferably 0.5～30g/10 minute scope is preferably 5～10g/10 minute scope especially.If MFR is in above-mentioned scope, the favorable dispersibility of low density ethylene-alpha olefin copolymer (F) then, gloss, the raising of low-temperature impact property.
In addition; Above-mentioned low density ethylene-alpha olefin copolymer (F) can be through obtaining ethene and alpha-olefin copolymer; But the polymer that ethene-alpha-olefin copolymer both can be to use the Ziegler-Natta catalyst polymerization to obtain, the polymer that also can be to use metallocene catalyst polymerisation to obtain.
＜nucleator (D)＞
Use nucleator (D) among the present invention.As nucleator (D), can enumerate the compound more than a kind that is selected from aromatic phosphonic acid ester compound, carboxylic metallic salt nucleator, polymer nucleator, sorbose alcohols nucleator and the inorganic compound nucleator.Nucleator (D) does not preferably make the foul smell of multilayered blow container worsen.Nucleator (D) can use a kind of separately, also can be also with two or more.
As above-mentioned aromatic phosphonic acid ester compound, be preferably with the compound shown in following formula [III] and/or [IV].
Among above-mentioned formula [III], [IV], R
1Be that carbon number is 1～10 divalent alkyl, R
2And R
3Be respectively that hydrogen atom or carbon number are 1～10 alkyl independently, M is the metallic atom of 1～3 valency, and n is 1～3 integer, and m is 1 or 2.
As the concrete example of the aromatic phosphonic acid ester compound shown in the general formula [III], can enumerate 2,2'-methylene-two (4, the 6-di-tert-butyl-phenyl) phosphate sodium, 2; 2'-ethylidene-two (4, the 6-di-tert-butyl-phenyl) phosphate sodium, 2,2'-methylene-two (4, the 6-di-tert-butyl-phenyl) phosphate lithium, 2; 2'-ethylidene-two (4, the 6-di-tert-butyl-phenyl) phosphate lithium, 2,2'-ethylidene-two (4-isopropyl-6-tert-butyl-phenyl) phosphate sodium, 2,2'-methylene-two (4-methyl-6-tert butyl phenyl) phosphate lithium, 2; 2'-methylene-two (4-ethyl-6-tert-butyl-phenyl) phosphate lithium, 2,2'-butylidene-two (4, the 6-3,5-dimethylphenyl) phosphate sodium, 2,2'-butylidene-two (4; The 6-di-tert-butyl-phenyl) phosphate sodium, 2, uncle's 2'-octyl group methylene-two (4, the 6-3,5-dimethylphenyl) phosphate sodium, 2, uncle's 2'-octyl group methylene-two (4; The 6-di-tert-butyl-phenyl) phosphate sodium, two (2,2'-methylene-two (4, the 6-di-tert-butyl-phenyl) phosphate) calcium, two [2,2'-methylene-two (4; The 6-di-tert-butyl-phenyl) phosphate] magnesium, two [2,2'-methylene-two (4, the 6-di-tert-butyl-phenyl) phosphate] barium, 2,2'-methylene-two (4-methyl-6-tert butyl phenyl) phosphate sodium, 2; 2'-methylene-two (4-ethyl-6-tert-butyl-phenyl) phosphate sodium, 2,2'-ethylidene-two (butyl between 4--6-tert-butyl-phenyl) phosphate sodium, 2,2'-methylene-two (4; The 6-3,5-dimethylphenyl) phosphate sodium, 2,2'-methylene-two (4,6-diethyl phenyl) phosphate sodium, 2; 2'-ethylidene-two (4, the 6-di-tert-butyl-phenyl) phosphate potassium, two [2,2'-ethylidene-two (4; The 6-di-tert-butyl-phenyl) phosphate] calcium, two [2,2'-ethylidene-two (4, the 6-di-tert-butyl-phenyl) phosphate] magnesium, two [2; 2'-ethylidene-two (4, the 6-di-tert-butyl-phenyl) phosphate] and barium, three [2,2'-methylene-two (4; The 6-di-tert-butyl-phenyl) phosphate] aluminium, three [2,2'-ethylidene-two (4, the 6-di-tert-butyl-phenyl) phosphate] aluminium and the two or more mixture in them etc.
As aromatic phosphonic acid ester compound, also can use the hydroxy Al phosphate compound shown in the general formula [IV], preferred especially R
2And R
3Be the compound shown in the general formula [V] of the tert-butyl group.
In formula [V], R
1Be that carbon number is 1～10 divalent alkyl, m is 1 or 2.Preferred especially aromatic phosphonic acid ester compound is the compound shown in the general formula [VI].
In formula [VI], R
1Be methylene or ethylidene.As the compound shown in the general formula [VI], particularly, for two [2,2-methylene-two (4; The 6-di-t-butyl) phosphate] hydroxy Al (another name: two (2,4,8; 10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3; Aluminium hydroxide salt dioxy phospha eight ring-6-oxides)) or two [2,2-ethylidene-two (4, the 6-di-t-butyl) phosphate] hydroxy Al 2].
As the carboxylic metallic salt nucleator, for example, can use p-tert-butyl benzoic acid aluminium salt, adipic acid aluminium, Sodium Benzoate.
Preferably use the branched alpha-olefine polymers as the polymer nucleator.Example as the branched alpha-olefine polymers; Can enumerate 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4; 4-dimethyl-1-hexene, 4; 4-dimethyl-1-amylene, 4-ethyl-1-hexene, the 3-ethyl-homopolymers of 1-hexene or the copolymer between them can also be enumerated the copolymer of the alpha-olefin of they and other.
These polymer nucleators can either directly cooperate when making polymerization of olefines compositions (E); Also can be when propylene resin (A) be made; Before the polymerization of propylene resin (A) or afterwards block ground carries out the polymerization of above-mentioned branched alpha-olefin, cooperates (note is made the polymer nucleator and cooperated propylene resin (A')) through use the propylene resin (A) that contains the branched alpha-olefine polymers as nucleator (D).When cooperating propylene resin (A') to use as the raw material of polymerization of olefines compositions (E) the polymer nucleator, it is the use level of the nucleator (D) in the polymerization of olefines compositions (E) that the polymer nucleator cooperates the amount of polymer nucleator contained in the propylene resin (A').The part that in addition, will cooperate the amount that deduct the polymer nucleator the propylene resin (A') from the polymer nucleator is as the propylene resin (A) in the polymerization of olefines compositions (E).
In addition, above-mentioned polymer nucleator can either use the prepolymerization of known method when making polymer (A), polymer (B), polymer (F) to form, and also can when making polymer (B), polymer (F), form through segment copolymerization method.
In addition, at this moment, also can and with polymer nucleator cooperation propylene resin (A') with do not contain the propylene resin (A) of polymer nucleator.In addition, also can also cooperate propylene resin (A') and other nucleator (D) with the polymer nucleator.
These polymer nucleators during other resinaes of after polymerization of olefines compositions (E) contains, stating, also can cooperate through when making polymerization of olefines compositions (E), using the masterbatch that contains other resinaes and polymer nucleator.When this masterbatch is used as the raw material of polymerization of olefines compositions (E), with the amount of polymer nucleator contained in the masterbatch use level as the nucleator (D) in the polymerization of olefines compositions (E).In addition, also can make the polymerization of olefines compositions also with masterbatch and other nucleators (D).
As the polymer nucleator, the viewpoint of good economy in, the polymer of preferred especially 3-methyl-1-butene from the characteristic of the transparency, low temperature resistance to impact, rigidity.
As sorbose alcohols nucleator, can preferably utilize 1,2,3-three deoxidations-4,6 ︰ 5,7-pair-O-[(4-propyl phenyl) methylene]-nonyl alcohol.
As the inorganic compound nucleator, for example can use talcum, mica, calcium carbonate.
Among these nucleators (D), from the viewpoint of the transparency, low temperature resistance to impact, rigidity and low foul smell, the preferred use is selected from 1,2; 3-three deoxidations-4,6 ︰ 5,7-pair-O-[(4-propyl phenyl) methylene]-nonyl alcohol and two (2; 4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d; G] [1,3,2] dioxy phospha eight ring-6-oxides) at least a kind of nucleator in the aluminium hydroxide salt.Among them, more preferably use two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] dioxy phospha eight ring-6-oxides) aluminium hydroxide salt.
As the nucleator that uses among the present invention (D), can use commercially available article, for example, ADKSTAB NA-21 (ADEKA corporate system) is as containing two (2; 4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1; 3,2] dioxy phospha eight ring-6-oxides) aluminium hydroxide salt is that the nucleator of principal component is commercially available, 1,2; 3-three deoxidations-4,6 ︰ 5,7-pair-O-[(4-propyl phenyl) methylene]-nonyl alcohol is commercially available with the trade name of MIRADE NX8000 (Miriken corporate system).
＜olefin polymer compositions (E)＞
The olefin polymer compositions that uses among the present invention (E) is the employed resin of outermost layer of multilayered blow container of the present invention; It is the composition that contains above-mentioned propylene resin (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions (wherein, (A) with (B) 100 weight portions that add up to) and nucleator (D) 0.01～0.5 weight portion.
In addition; When multilayered blow container of the present invention needs the low temperature resistance to impact; As stated; As olefin polymer compositions (E), the preferred composition that also contains low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion at propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D) in addition that uses.
In addition, when multilayered blow container did not need the low temperature resistance to impact, also preferred olefin polymers composition (E) was the composition that does not contain low density ethylene-alpha olefin copolymer (F).
The use amount of propylene resin (A) and ethene-alpha-olefin copolymer (B); From the good viewpoint of being clamminess property and the viewpoint of economy and productivity ratio; Preferred aforesaid propylene resinoid (A) is 95.5～98 weight portions; Above-mentioned ethene-alpha-olefin copolymer (B) be 2～4.5 weight portions (wherein, (A) with (B) add up to 100 weight portions).
The aforesaid propylene resinoid (A) that uses in order to obtain olefin polymer compositions (E) is more than 98 weight portions; When above-mentioned ethene-alpha-olefin copolymer (B) is less than 2 weight portions; The resistance to impact of multilayered blow container, poor with the cementability of other layers, the aforesaid propylene resinoid (A) that cooperates in the olefin polymer compositions (E) is less than 80 weight portions, and above-mentioned ethene-alpha-olefin copolymer (B) is during more than 20 weight portions; Generation is clamminess, so not preferred.
In addition, when multilayered blow container needed the low temperature resistance to impact, from the viewpoint that is clamminess with economy, the above-mentioned low density ethylene-alpha olefin copolymer (F) that is cooperated in the preferred olefin polymers composition (E) was 3～15 weight portions.
Through measuring 100 weight portions, use the nucleator (D) of 0.01～0.5 weight portion, the effect of the glossiness of the multilayered blow container that can be improved with respect to the total of propylene resin (A) and ethene-alpha-olefin copolymer (B).If the addition of nucleator (D) is less than 0.01 weight portion, the effect that then improves glossiness is little.Even the addition that adds nucleator (D) is more than 0.5 weight portion, not only effect does not change, and unfavorable economically yet, so not preferred.
Above-mentioned olefin polymer compositions (E) satisfies following condition (E-1).
(E-1), be 5～10g/10 minute scope to measure melt flow rate (MFR) (MFR) that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.If MFR is in above-mentioned scope, then the flowability of the olefin polymer compositions (E) during moulding is being suitable for the scope of moulding, the fine melt fracture (MF) that takes place in the time of can suppressing moulding.In addition, the uneven thickness of the olefin polymer compositions (E) of blow molding can be prevented, the excellent multilayered blow container of flatness can be accessed.
According to ASTM D-1238, to measure melt flow rate (MFR) (MFR) that 230 ℃ of temperature, 2.16kg load record if be higher than 10g/10 minute, insufficient formability then, if be lower than 5g/10 minute, then glossiness is poor.
The condition (E-1) relevant with olefin polymer compositions (E); Promptly according to ASTM D-1238; With the melt flow rate (MFR) (MFR) that 230 ℃ of temperature of mensuration, 2.16kg load record, can adjust through the suitable low density ethylene-alpha olefin copolymer (F) of propylene resin (A), ethene-alpha-olefin copolymer (B) and the use as required of use of selecting.
The propylene resin (A) and the ethene-alpha-olefin copolymer (B) that use; According to ASTMD-1238; When all being 5～10g/10 minute scope to measure melt flow rate (MFR) (MFR) that 230 ℃ of temperature, 2.16kg load record, can be through the condition of suitably selecting propylene resin (A), ethene-alpha-olefin copolymer (B) and the low density ethylene-alpha olefin copolymer (F) that uses as required to come satisfied (E-1).
In addition; Under situation in addition; For example; As propylene resin (A), to use according to ASTM D-1238, the melt flow rate (MFR) (MFR) that records with 230 ℃ of temperature of mensuration, 2.16kg load is under the situation less than propylene resin about 5g/10 minute, that MFR is lower; By propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D) and the low density ethylene-alpha olefin copolymer (F) that uses as required when forming olefin polymer compositions (E); Can be through in the presence of organic peroxide, carrying out melting mixing, and carry out propylene resin (A), ethene-alpha-olefin copolymer (B), or the modification of low density ethylene-alpha olefin copolymer (F) of using as required, the MFR of olefin polymer compositions (E) is adjusted in the above-mentioned scope.Wherein, as organic peroxide, can enumerate with above-mentioned＜propylene resin (A)＞the identical material put down in writing of project.
In addition; As other examples; When using MFR to surpass 10g/10 minute MFR as propylene resin (A) than higher propylene resin; Can be through using the low copolymer of MFR as the ethene-alpha-olefin copolymer (B) of combination, low density ethylene-alpha olefin copolymer (F) of using as required, the MFR of olefin polymer compositions (E) is adjusted in the above-mentioned scope.
The crystalline melting point that above-mentioned olefin polymer compositions (E) preferably records with DSC according to JIS-K7121 is 140～155 ℃ a scope.When crystalline melting point is in above-mentioned scope, can access the multilayered blow container that gloss is good, resistance to impact is good.
The crystalline melting point of above-mentioned olefin polymer compositions (E) can use differential scanning calorimetry (DSC) (DSC) to measure according to JIS-K7121.Particularly, can be to measure with the same method of the crystalline melting point of aforesaid propylene resinoid (A).
In addition, the preferred hypocrystalline time (t of above-mentioned olefin polymer compositions (E)
1/2) be 50～1000 seconds scope, 100～500 seconds scope more preferably.In above-mentioned scope, mould transfer printing property is good when blow molding, can access the good multilayered blow container of gloss.
Wherein, hypocrystalline time (t
1/2), can measure the thermal discharge of accompanying crystallizationization this moment as under 125 ℃ of isothermys, making olefin polymer compositions (E) crystallization, begin (crystallization begins) from heat release and measure to the time that thermal discharge reaches till half the value of total thermal discharge.
Hypocrystalline time (the t of above-mentioned olefin polymer compositions (E)
1/2) amount of the nucleator (D) that can be contained through olefin polymer compositions (E) adjusts.Amount through increasing the nucleator (D) that olefin polymer compositions (E) contained can be accelerated hypocrystalline time (t
1/2), otherwise, can postpone hypocrystalline time (t through the amount that reduces nucleator (D)
1/2).
In the olefin polymer compositions of the present invention (E), also can contain aforesaid propylene resinoid (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and nucleator (D) composition in addition.
As above-mentioned (A), (B), (F) and (D) in addition composition, can enumerate other resinae, various additives etc.
As other resinae, can enumerate for example propylene resin (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and nucleator (D) polyolefin resin in addition.As polyolefin resin, can illustration propylene resin (A) propylene resin (P) in addition.As propylene resin (P), can enumerate the homopolymers (comprising syndiotactic propylene homopolymers etc.) of the propylene different etc. with propylene resin (A).Usually, the Tm that records with differential scanning calorimetry (DSC) (DSC) according to JISK7121 of propylene resin (P) is 140～155 ℃.In addition, as propylene resin (P) according to ASTM D-1238 to measure the MFR that 230 ℃ of temperature, 2.16kg load record, be preferably 0.01～20g/10 minute, be preferably 0.1～5g/10 minute especially.
In addition, as other resins, for example also can illustration phenylethylene elastomer or its hydride (S).In addition, when hope reduced gloss to the dependence of die surface roughness, preferred mode was not add phenylethylene elastomer or its hydride (S).
As phenylethylene elastomer or its hydride (S); Can enumerate styrene-content 10～70 weight %, preferred 10～65 weight %, more preferably 10～40 weight % and conjugated diene content 30～90 weight %, preferred 35～90 weight %, more preferably phenylethylene elastomer or its hydride (S) of 60～90 weight %.
As above-mentioned phenylethylene elastomer or its hydride (S); Can enumerate contain styrenic polymer block composition (below; Sometimes be also referred to as styrene block) and SBC, styrene butadiene random copolymer, styrene-isoprene random copolymer, styrene-chlorobutadiene random copolymer and their hydride etc. of conjugated diolefine polymer block composition (below, be also referred to as diene block sometimes).Optimization styrene based block copolymer among them.
The styrenic polymer block composition that constitutes above-mentioned SBC is made up of the styrene or derivatives thereof; As the concrete material of monomer, can enumerate styrene, AMS, p-methylstyrene, chlorostyrene, vinyl naphthalene etc.Optimization styrene among them.These monomers can use a kind of separately, or combination is used two or more.
As the concrete material of the monomer that constitutes above-mentioned conjugated diolefine polymer block, can enumerate butadiene, isoprene, chlorobutadiene etc.Preferred butadiene, isoprene among them.These monomers can use a kind of separately, or combination is used two or more.
The styrene block in the SBC and the combination of diene block are not special to be limited, but optimization styrene block-diene block or styrene block-[diene block-styrene block]
nThe mode of (wherein, n is 1～5).
The content of hoping the styrenic polymer block composition in the SBC is 10～70 weight %; Be preferably 10～65 weight %; 10～40 weight % more preferably; The content of hoping conjugated diolefine polymer block composition is 30～90 weight %, is preferably 35～90 weight %, more preferably 60～90 weight %.
Hope that SBC is more than the 0.1g/10min, to be preferably 0.3～20g/10min according to ASTM D-1238, with 230 ℃, the melt flow rate (MFR) (MFR) that records of load 2160g, is preferably 5～10g/10min especially.
As the object lesson of SBC, can enumerate styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), SBS (SBS), SIS (SIS) and styrene-ethylene-propylene-based block copolymer (SEP) etc.
When olefin polymer compositions (E) contains other resinaes; With respect to above-mentioned (A) and 100 weight portions of total (B), the upper limit is generally below 20 weight portions, more preferably below 10 weight portions; Be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
As other resins; When using aforesaid propylene resinoid (P); Aforesaid propylene resinoid (P) is with respect to above-mentioned (A) and 100 weight portions of total (B), and the upper limit is generally below 20 weight portions, more preferably below 10 weight portions; Be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
As other resins; When using above-mentioned phenylethylene elastomer or its hydride (S), above-mentioned phenylethylene elastomer or its hydride (S) are with respect to above-mentioned (A) and 100 weight portions of total (B); The upper limit is generally below 20 weight portions; More preferably below 10 weight portions, be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
As other resins; When using at least a in aforesaid propylene resinoid (P) and above-mentioned phenylethylene elastomer or its hydride (S), the total of aforesaid propylene resinoid (P) and above-mentioned phenylethylene elastomer or its hydride (S) is with respect to above-mentioned (A) and 100 weight portions of total (B); The upper limit is generally below 20 weight portions; More preferably below 10 weight portions, be more preferably below 5 weight portions, lower limit is generally 0.1 weight portion.
In addition; Under hoping that gloss is to the little situation of the dependence of die surface roughness; The mode of do not add the mode of aforesaid propylene resinoid (P), not adding above-mentioned phenylethylene elastomer or its hydride (S) is the mode of more hoping, the mode of not adding aforesaid propylene resinoid (P) and above-mentioned phenylethylene elastomer or its hydride (S) is the mode of hoping more.
In addition, when stating phenylethylene elastomer or its hydride (S) in the use, from the viewpoint that is clamminess, it is one of preferred mode that above-mentioned low density ethylene-alpha olefin copolymer (F) exists on a small quantity or not.
When not using above-mentioned low density ethylene-alpha olefin copolymer (F); Use is by aforesaid propylene resinoid (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions (wherein, (A) with (B) 100 weight portions that add up to) and to be selected from as the Tm of composition arbitrarily be that 140～155 ℃ the propylene resin (P) and the polymerization of olefines compositions (E) of at least a polymer 0～20 weight portion in phenylethylene elastomer or its hydride (S) (for the amount with respect to (A) and 100 weight portions of total (B)) formation in fact also are one of optimal ways of the present invention.Comprise also that wherein Tm is that 140～155 ℃ the propylene resin (P) and the total of phenylethylene elastomer or its hydride (S) are the situation of 0 weight portion with respect to (A) and 100 weight portions of total (B).Wherein, it is expression polymerization of olefines compositions (E) that what is called forms in fact, as other compositions, also can contain additive in the scope of not damaging effect of the present invention, but does not comprise the composition beyond it.
As additive, can enumerate anti-oxidant, hydrochloric acid absorbent, heat-resisting stabilizing agent, light stabilizer, ultra-violet absorber, lubricant, antistatic additive, fire retardant, pigment, dyestuff, dispersant, copper evil and prevent that agent, nertralizer, blowing agent, plasticizer, bubble from preventing fluidity amendment, weld strength modifying agent of agent, crosslinking agent, peroxide etc. etc.As these additives, not special the qualification for example can be used commercially available article.
At olefin polymer compositions (E) when containing additive; As the amount of additive, as long as be the amount that can obtain the scope of effect of the present invention, not special the qualification; But, be generally 0.01～1.00 weight portion with respect to above-mentioned (A) and 100 weight portions of total (B).
The olefin polymer compositions that uses among the present invention (E); Because MFR is specific scope; Therefore it is difficult only carrying out blow molding with olefin polymer compositions (E), but can use as the top layer of multi-layer blow molding body, through using as the top layer; Show excellent gloss, have excellent rerum natura.
Not special qualification of preparation method as olefin polymer compositions (E); Method for example can be listed below: with propylene resin (A), ethene-alpha-olefin copolymer (B) and nucleator (D), can arbitrarily used low density ethylene-alpha olefin copolymer (F), other resinaes and additive drop in the mixers such as Henschel mixer, Banbury, rotary drum mixer and mix; Then; Resulting mixture through extruder moulding such as single screw extrusion machine, double screw extruders, is obtained the line material of olefin polymer compositions (E).In addition, before carrying out blow molding, use comminutor etc. is shaped to pellet to above-mentioned line material usually.
In addition; When using the additive of peroxide such as organic peroxide, crosslinking agent isoreactivity as above-mentioned additive; When utilizing above-mentioned mixer to mix, also can follow propylene resin (A), ethene-alpha-olefin copolymer (B), the modification of employed low density ethylene-alpha olefin copolymer (F) as required.
In addition; Use the formed multilayered blow container of olefin polymer compositions (E) to show that the reason of good rerum natura is still indeterminate as forming outermost resin; But can think the ethene-alpha-olefin copolymer (B) that has the crystalline melting point of particular range through use; Ethene-alpha-olefin copolymer (B) carries out differential to propylene resin (A) and looses, therefore, and the gloss of resulting multilayered blow container, appearance excellence; Resistance to impact improves, and can take into account resistance to impact and low being clamminess property.In addition; Can think as the polymer that forms the internal layer that joins with outermost layer; When acronal of stating after the use (G) or polyvinyls (H); Because ethene-alpha-olefin copolymer (B) differential as this layer and outermost adhesive spots looses, so the number of adhesive spots increases, with the cementability of internal layer also excellence.In addition, can think, when using low density ethylene-alpha olefin copolymer (F); Jie at ethene-alpha-olefin copolymer (B) is descending; Low density ethylene-alpha olefin copolymer (F) differential in propylene resin (A) looses, so gloss, appearance are excellent, resistance to impact and the raising of low temperature resistance to impact; And can think that therefore being clamminess property also can suppress very lowly because differential looses.
＜multilayered blow container＞
Multilayered blow container of the present invention, the employed resin of outermost layer comprises above-mentioned olefin polymer compositions (E).Multilayered blow container of the present invention has at least one internal layer as the layer beyond the outermost layer.
Do not limit as other layers (internal layer) that form multilayered blow container are special, constitute by olefin polymer compositions (E) thermoplastic resin in addition usually.
As olefin polymer compositions (E) thermoplastic resin in addition; Can enumerate acronal (G), polyvinyls (H), styrenic polymer, pet resin, polyamide, ABS resin, ethene-vinyl acetate copolymer, polyvinyl alcohol resin or Corvic, Corvic and modified polyolefin resin etc., also can use the mixture of the above-mentioned resin more than 2 kinds.Wherein, preferred acronal (G), polyvinyls (H).
Wherein, acronal (G) is meant the acronal with the above construction unit from propylene of 51 moles of %, and polyvinyls (H) is meant the polyvinyls with the above construction unit from ethene of 51 moles of %.
Multilayered blow container have as other layers (internal layer) by styrenic polymer or pet resin, polyamide, ABS resin, ethene-vinyl acetate copolymer, polyvinyl alcohol resin, Corvic isopolarity resin forms layer time; Viewpoint from the adhesive strength of interlayer; Preferably, have by the formed layer of modified polyolefin resin (I) at outermost layer and between by styrenic polymer or the formed layer of polar resin.
The outermost layer of multilayered blow container of the present invention is a high glaze by the formed layer of olefin polymer compositions (E) promptly.In addition, the resistance to impact of multilayered blow container is also excellent.
The outermost layer of multilayered blow container of the present invention, promptly by the formed layer of olefin polymer compositions (E), the MFR as the liquidity scale of olefin polymer compositions (E) is specific scope.Therefore, can infer in blow molding that the surface of the heating and melting resin before soon contacting with mould becomes smoothly easily, the surface also becomes smoothly easily after blow molding, can think, can access the excellent multilayered blow container of lustrous surface property thus.In addition, because the MFR as the liquidity scale of olefin polymer compositions (E) is specific scope, so appearance is also good.
In addition, olefin polymer compositions (E) can use ethene-alpha-olefin copolymer (B) as the raw material of said composition.Because above-mentioned ethene-alpha-olefin copolymer (B) has the crystalline melting point of particular range; Therefore resulting formed body is except showing that above-mentioned adhesiveness between layers is excellent, being clamminess property is low etc. the excellent specific property; Ethene-alpha-olefin copolymer (B) with respect to the few situation of the use amount of propylene resin (A) under, also can improve resistance to impact efficiently.Its reason confirms as yet, but can infer, the ethene-alpha-olefin copolymer (B) of the fusing point through selecting to have particular range, and the layer thickness with appropriateness, articulamentum also be an optimum with the amount of the tie molecule (tiemolecular) of layer.
In addition, olefin polymer compositions (E) as the raw material of said composition, can use low density ethylene-alpha olefin copolymer (F) as required.Above-mentioned low density ethylene-alpha olefin copolymer (F) with respect to the few situation of the use amount of propylene resin (A) under, also can improve the low temperature resistance to impact efficiently.
According to above content, inventor of the present invention infers that multilayered blow container of the present invention is a high glaze, and resistance to impact is excellent simultaneously, and the low temperature resistance to impact is also excellent when stating low density ethylene-alpha olefin copolymer (F) in the use.
Multilayered blow container of the present invention, resistance to impact is excellent, therefore can suppress by breaking of causing of the impact from the outside etc., and outermost layer is a high glaze, so container has the glossiness that transparent feel is arranged.In addition, multilayered blow container of the present invention is because the low temperature resistance to impact is excellent, therefore in multilayered blow container, is filled with content and under cryogenic conditions, transports, under the situation such as storage, also can suppress by breaking of causing of the impact from the outside etc.
Layer structure as multilayered blow container of the present invention; As long as outermost layer is for comprising the layer of olefin polymer compositions (E); Not special the qualification; For example can enumerate the two-layer structure (with the layer structure of the arranged in order of outermost layer/innermost layer) of the outermost layer that comprises olefin polymer compositions (E) and innermost layer; Comprise olefin polymer compositions (E) outermost layer, with the adjacent intermediate layer of this outermost layer and with the three-decker of the adjacent innermost layer in this intermediate layer (with the layer structure of the arranged in order of outermost layer/intermediate layer/innermost layer), comprise olefin polymer compositions (E) outermost layer, with the adjacent intermediate layer (1) of this outermost layer, and adjacent intermediate layer (2), this intermediate layer (1) and with the four-layer structure of this intermediate layer (2) adjacent innermost layer (with the layer structure of the arranged in order of outermost layer/intermediate layer (1)/intermediate layer (2)/innermost layer) etc.
Wherein, in the present invention, will be positioned at the inboard layer of outermost layer and be defined as internal layer.That is, in the present invention, above-mentioned innermost layer, intermediate layer are equivalent to internal layer, and multilayered blow container of the present invention has one deck internal layer at least, also can have internal layer more than two layers.
Have in the multilayered blow container of the present invention of olefin polymer compositions (E) at outermost layer; With the adjacent layer of outermost layer by acronal (G) or polyvinyls (H) when forming, even do not use so-called adhering resin also to show firm cementability.From with the viewpoint of the outermost cementability that comprises olefin polymer compositions (E) of multilayered blow container of the present invention, preferably be acronal (G) or polyvinyls (H) with the adjacent layer of the outermost layer that comprises olefin polymer compositions (E).
In addition; With the adjacent layer of olefin polymer compositions (E) be aforesaid propylene base polymer (G) and polyvinyls (H) in addition layer time; From with the viewpoint of the outermost cementability that comprises olefin polymer compositions (E); Preferably, form the outermost layer and other layers that comprise olefin polymer compositions (E) across the adhesive resin layer.
Multilayered blow container of the present invention, layer can be by painted arbitrarily for it.
As aforesaid propylene base polymer (G), not special the qualification can be enumerated homo-polypropylene, propylene-alpha-olefin random copolymer, propylene-alpha-olefin block copolymer etc.As acronal (G) according to ASTM D-1238, to measure the MFR that 230 ℃ of temperature, 2.16kg load record, be preferably 0.1～20.0g/10 minute scope, be preferably 0.1～5g/10 minute especially.The crystalline melting point that preferably records with differential scanning calorimetry (DSC) (DSC) according to JIS-K7121 in addition is 100～168 ℃ a scope.
As above-mentioned polyvinyls (H), not special the qualification can be enumerated so-called high density polyethylene (HDPE), straight chain shape low density polyethylene (LDPE), low density polyethylene (LDPE).Polyvinyls (H) is preferably 0.860～0.980g/cm with the density that the density gradient column method records
3, in addition as according to ASTM D-1238 to measure the MFR that 230 ℃ of temperature, 2.16kg load record, preferred 0.01～20g/10 minute, be preferably 0.1～5g/10 minute especially.
As above-mentioned modified polyolefin resin (I), not special the qualification generally can be used acid modified polyolefin.The acid that acid is used in the modification for example can be enumerated vinyl unsaturated carboxylic acid or its acid anhydrides of maleic anhydride, acrylic acid, methacrylic acid, itaconic anhydride and so on.In addition, as the vistanex that uses in the modification, optimal ethylene-alpha olefin copolymer, Noblen, propylene-alpha-olefin copolymers.
In addition, in the multilayered blow container, be preferably by acronal (G), polyvinyls (H), styrenic polymer with internal layer beyond the adjacent layer of outermost layer or be selected from that at least a kind resin in pet resin, polyamide, ABS resin, ethene-vinyl acetate copolymer, polyvinyl alcohol resin or the Corvic forms layer.
In addition, also can contain other resinaes, various additive in the layer beyond the outermost layer.
As the method for forming of multilayered blow container of the present invention,, can be any method so long as blow molding gets final product.As the method for forming, can enumerate direct blow molding method (hollow molding method), injection stretch blow molding method (injection hollow molding method), extrude stretch blow-molded method, sheet material blow molding method etc.As multilayered blow container, the viewpoint of the productivity ratio when producing in a large number, the container that preferably obtains through direct blow molding method or the moulding of injection stretch blow molding method.
When being shaped to multilayered blow container through direct blow molding method; For example, use multilayer blow moulding to use mould, with olefin polymer compositions (E) and other resins so that olefin polymer compositions (E) is outermost mode; With tubular extruded; During resulting parison also is in molten condition, clamp with blow mold, in parison, be blown into fluid and be shaped to the regulation shape.Because the layer that is formed by olefin polymer compositions (E) is outermost layer, therefore can access the multilayered blow container of high glaze.
And; (E) in view of its MFR; The situation (for example slightly having any problem sometimes in the big blow molding) that in blow molding, is restricted is arranged in the time of separately; If but used the application's technology, through the layer beyond the suitable selection outermost layer (for example through suitably selecting (G) or (H)), also could realize gloss etc. simultaneously and maximize etc.
Though condition of molding also depends on the proterties of resin, the temperature of the resin when preferably being blown into fluid, i.e. moulding temperature is 120～260 ℃, the pressure that is blown into of preferably fluid is 2～10kg/cm
2, consider that from the viewpoint of mouldability preferred blowing ratio is 1.2～5.0.
Here the value that said blowing obtains divided by the external diameter of the tubular molten parison of being extruded by extruder die portion than the external diameter of the bottle that is meant moulding.
When being shaped to multilayered blow container, for example,,, be shaped to young base through injection moulding so that olefin polymer compositions (E) is outermost mode through with olefin polymer compositions (E) and other resins through the injection stretch blow molding method.Then, be under the situation of molten condition or soft state at this young bird base, young base is solidified after again after the heating; Use stretching rod etc. should the young bird base longitudinal stretching by the strong hand; Then for again at cross directional stretch, in young base, be pressed into pressure fluid, can access multilayered blow container thus.Through injection moulding during with young blank molding, the injection temperature of olefin polymer compositions (E) is generally 160～260 ℃ scope.Be about to carry out the preceding young base temperature of above-mentioned longitudinal stretching and be preferably 110～150 ℃, the longitudinal stretching multiplying power is preferably 1.5～4.0 times, and the cross directional stretch multiplying power is preferably 1.5～3.0 times.
The thickness of multilayered blow container of the present invention, size can be according to the suitably decisions such as purposes of multilayered blow container, but thickness is 0.3～10.0mm usually, is of a size of diameter 10～300mm, height 10～300mm.
The thickness of the preferred outer internal layer with other of the outermost thickness of multilayered blow container of the present invention is more preferred 50/50～5/95 than (skin/internal layer), and more preferably 30/70～10/90.In above-mentioned scope, outer field high glaze is easy to performance most, and mouldability is also good, so preferred.
Multilayered blow container of the present invention, when the layer beyond outermost layer also used transparent resin, the transparency was excellent.Particularly, preferably according to JIS-K7105, the mist value (turbidity) of using nephelometer to record is below 30, more preferably below 20.In the time of in above-mentioned scope, can access the visibility bottle very good, that surcharge is high of content.
Multilayered blow container gloss of the present invention is excellent, and particularly, preferred outermost layer is more than 70 according to JIS-K7105 with the 60 degree glossiness that gloss meter records, more preferably more than 75.When above-mentioned scope, can access the high bottle of glossy appearance, surcharge that shows excellence.
Multilayered blow container of the present invention can use in various uses; For example be suitable as the container of food such as filling sauce, baste, fruit juice, fruit, dessert, poach vegetables, be suitable as the container of the amenities such as container, filling liquid lotion of Toiletries such as filling cosmetics, shampoo.
[manufacturing approach of multilayered blow container]
The manufacturing approach of multilayered blow container of the present invention; Preferred use above-mentioned olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin composition in addition; Form outermost layer with above-mentioned olefin polymer compositions (E); Above-mentioned olefin polymer compositions (E) thermoplastic resin composition in addition forms the mode of at least one internal layer, carries out moulding through direct blow molding method or injection stretch blow molding method.
As the propylene resin that uses in the manufacturing approach of the present invention (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F), nucleator (D), olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin in addition; The material of in the project of above-mentioned [multilayered blow container], explaining be can use, other resinaes of in the project of [multilayered blow container], explaining, various additive also can be used.
In manufacturing approach of the present invention, through direct blow molding method or injection stretch blow molding method, the multilayered blow container moulding that outermost layer is formed by olefin polymer compositions (E).Therefore, therefore the multilayered blow container that obtains is high glaze owing to the outermost layer at this multilayered blow container contains ethene-alpha-olefin copolymer (B).In addition, multilayered blow container is also excellent on resistance to impact.
The multilayered blow container that obtains through manufacturing approach of the present invention, because resistance to impact is excellent, so suppressed by breaking of causing of the impact from the outside etc., because outermost layer is a high glaze, container has the glossiness that transparent feel is arranged.
Embodiment
Then, expression embodiment illustrate in greater detail the present invention, but the present invention is not limited by these embodiment.
[manufacturing of propylene resin (A-1)]
(1) preparation of solid catalyst component
Anhydrous magnesium chloride 95.2g, decane 442ml and 2-Ethylhexyl Alcohol 390.6g are carried out after 2 hours reacting by heating process homogeneous solution at 130 ℃; In this solution, add phthalic anhydride 21.3g; Carry out mixing in 1 hour at 130 ℃ again, make the phthalic anhydride dissolving.
Behind the homogeneous solution cool to room temperature that operation obtains like this, this homogeneous solution 75ml was added dropwise among the titanium tetrachloride 200ml that remains in-20 ℃ with 1 hour.After add finishing, the temperature of this mixed liquor is warmed up to 110 ℃ with 4 hours, when reaching 110 ℃, adds diisobutyl phthalate (DIBP) 5.22g, stir maintenance 2 hours in this temperature thus.
After 2 hours reaction finishes, collect solid part through heat filtering, make this solid part outstanding more turbid in the titanium tetrachloride of 275ml after, again 110 ℃ of heating 2 hours.After reaction finishes, collect solid part through heat filtering again, fully clean, up in solution, detecting the titanium compound of not going on a tour and leaving with 110 ℃ decane and hexane.With the solid part after cleaning as solid titanium catalyst component (A).Solid titanium catalyst component (A) is preserved as the decane slurry, but from studying the purpose that catalyst is formed, a part wherein is dry.Above-mentioned solid titanium catalyst component (A) consist of titanium 2.3 weight %, chlorine 61 weight %, magnesium 19 weight %, DIBP12.5 weight %.
Wherein, the detection of above-mentioned free titanium compound is carried out with following method.In the Schlenk reactor of the 100ml of nitrogen displacement in advance band branch, collect the supernatant 10ml that adds above-mentioned solid catalyst component with syringe.Then, through nitrogen fluidized drying solvent hexane, vacuum drying is 30 minutes again.Add deionized water 40ml, 50 capacity % sulfuric acid 10ml therein, stirred 30 minutes.This aqueous solution through filter paper, is transferred in the 100ml volumetric flask, then, as the screening agent adding conc.H of iron (II) ion
3PO
41ml, and add 3%H as the colour reagent of titanium
2O
2Aqueous solution 5ml is adjusted into 100ml with deionized water with volume again.Vibration mixes this volumetric flask, after 20 minutes, uses the absorbance of UV observation 420nm, the detection of the titanium that dissociates.The cleaning of the titanium that dissociates is removed and the detection of the titanium that dissociates, till not observing this absorption.
(2) preparation of pre-polymerized catalyst composition
With the there-necked flask that has mixer of internal volume 500ml with nitrogen replacement after, add heptane 400ml, triethyl aluminum 19.2mmol, dicyclopentyl dimethoxyl silane 3.8mmol, above-mentioned solid titanium catalyst component (A) 4g through processed.Internal temperature is remained on 20 ℃, and the speed with 8g/hr imports propylene gas continuously while stirring.After 1 hour, stop to stir the result has obtained every 1g solid titanium catalyst component (A) polymerization pre-polymerized catalyst composition (B) of 2g propylene.
(3) polymerization
After the stainless steel autoclave that has mixer of internal volume 10L is fully dry, nitrogen is replaced, add heptane 6L, triethyl aluminum 12.5mmol, dicyclopentyl dimethoxyl silane 0.6mmol through processed.Behind the nitrogen in the propylene displacement system, add hydrogen 0.30MPa-G, then import propylene and ethene while stirring.In addition, the adjustment import volume makes the ethylene concentration of the gas phase portion that polymerization tank is interior reach 1.5mol%.
After being stabilized in 80 ℃ of internal temperatures, stagnation pressure 0.8MPa-G in the system; Adding converts in the Ti atom and contains the heptane slurry 20.8ml of above-mentioned pre-polymerized catalyst composition (B) 0.10mmol; Mode limit to keep stagnation pressure and ethylene concentration is supplied with propylene and ethene continuously, and polymerization in 3 hours is carried out at 80 ℃ in the limit.
Stopping reaction, lower the temperature, take off pressure through the methyl alcohol that adds 50ml after the stipulated time.Content all is transferred to the lautertuns that has filter, is warming up to 60 ℃ and carries out Separation of Solid and Liquid.Clean 2 solid part with 60 ℃ heptane 6L again.With operating propylene/ethylene copolymer (propylene resin (the A-1)) vacuum drying that obtains like this.
The melt flow rate (MFR) (MFR) of resulting propylene resin (A-1) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 7.0g/10 minute, will by
13Weight from the construction unit of ethene that C-NMR calculates, when being made as 100 weight % from the construction unit of propylene with from the total of the construction unit of ethene is 3.2 weight %; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 145 ℃, Mw/Mn (molecular weight distribution) is 5.3.
[manufacturing of propylene resin (A-2)]
In the manufacturing of acronal (A-1), the ethylene concentration that is adjusted into the gas phase portion in the polymerization tank is 2.2mol%, in addition, carries out polymerization with the same operation of the manufacturing of acronal (A-1).
The melt flow rate (MFR) (MFR) of resulting propylene resin (A-2) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 7.0g/10 minute, will by
13Weight from the construction unit of ethene that C-NMR calculates, when being made as 100 weight % from the construction unit of propylene with from the total of the construction unit of ethene is 4.8 weight %; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 136 ℃, Mw/Mn (molecular weight distribution) is 5.5.
[manufacturing of propylene resin (A-3)]
In the manufacturing of acronal (A-1), the ethylene concentration that is adjusted into the gas phase portion in the polymerization tank is 0.8mol%, in addition, carries out polymerization with the same operation of the manufacturing of acronal (A-1).
The melt flow rate (MFR) (MFR) of resulting propylene resin (A-3) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 7.0g/10 minute, will by
13Weight from the construction unit of ethene that C-NMR calculates, when being made as 100 weight % from the construction unit of propylene with from the total of the construction unit of ethene is 1.0 weight %; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 156 ℃, Mw/Mn (molecular weight distribution) is 5.0.
[manufacturing of propylene resin (A-4)]
In the manufacturing of acronal (A-1), behind the nitrogen in the propylene displacement system, the hydrogen 0.15MPa-G that packs in addition, carries out polymerization with the same operation of the manufacturing of acronal (A-1).
The melt flow rate (MFR) (MFR) of resulting propylene resin (A-4) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 3.0g/10 minute, will by
13Weight from the construction unit of ethene that C-NMR calculates, when being made as 100 weight % from the construction unit of propylene with from the total of the construction unit of ethene is 3.2 weight %; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 145 ℃, Mw/Mn (molecular weight distribution) is 5.3.
[manufacturing of propylene resin (A-5)]
In the manufacturing of acronal (A-1), behind the nitrogen in the propylene displacement system, add hydrogen 0.45MPa-G, in addition, carry out polymerization with the same operation of the manufacturing of acronal (A-1).
The melt flow rate (MFR) (MFR) of resulting propylene resin (A-5) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 15.0g/10 minute, will by
13Weight from the construction unit of ethene that C-NMR calculates, when being made as 100 weight % from the construction unit of propylene with from the total of the construction unit of ethene is 3.2 weight %; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 145 ℃, Mw/Mn (molecular weight distribution) is 5.3.
[manufacturing of ethene-alpha-olefin copolymer (B-1)]
(1) Preparation of catalysts
In 300 liters reactor of fully nitrogen displacement, be added in 600 ℃ of dryings 10 hours silica 1 0.0kg and 154 liters of toluene processes and hangs turbid shape, is cooled to 0 ℃.Then, in this suspension, with 23.4 liters of the toluene solutions (Al=3.02 mol) that dripped MAO in 1 hour.At this moment, the temperature in the system is remained on 0～5 ℃ scope.
Then make its reaction 30 minutes, be warming up to 95 ℃ with 1.5 hours then, make its reaction 4 hours in this temperature at 0 ℃.Be cooled to 60 ℃ then, remove supernatant through decantation.After the solid constituent that obtains of operation cleaned 2 times with toluene like this, outstanding more turbid with 100 liters of toluene, making total amount was 160 liters.
In the suspension that like this operation obtains, 35 ℃ with 20.0 liters of the toluene solutions that dripped two (1,3-normal-butyl methyl cyclopentadienyl) zirconium dichlorides in 30 minutes (Zr=25.6 mM/liter), make its reaction 2 hours at 35 ℃ again.Then, remove supernatant,, obtain the solid catalyst component (1) that every 1g solid catalyst component contains the 3.2mg zirconium through cleaning 2 times with hexane.
(2) preparation of pre-polymerized catalyst composition
In 350 liters reactor of fully nitrogen displacement, pack into the above-mentioned solid catalyst component that makes (1) 7.0kg and hexane, making total measurement (volume) is 285 liters.After being cooled to 10 ℃ in the system, with ethene with 8Nm
3The flow of/hr is blown into 5 minutes in hexane.Therebetween, the temperature in the system remains on 10～15 ℃.Then, stop ethene and supply with, 2.4 moles of diisobutyl aluminium hydrides of packing into (DIBALH) and 1-hexene 1.2kg.Make in the system to behind the enclosed system, with 8Nm
3The flow of/hr begins the supply of ethene once more.After 15 minutes, the flow of ethene is dropped to 2Nm
3/ hr, making the pressure in the system is 0.08MPaG.Therebetween, the temperature in the system rises to 35 ℃.Then, the limit is 32～35 ℃ with the adjustment in the system, and the limit is with 4Nm
3The flow of/hr is supplied with 3.5 hours ethene.Therebetween, the pressure in the system remains on 0.07～0.08MPaG.Then, after replacing through nitrogen in the system, remove supernatant, clean 2 times with hexane.Operation like this, the pre-polymerized catalyst (2) of 3g polymer that obtained the prepolymerization of every 1g solid catalyst component.
(3) polymerization
Use continous way thermopnore gas phase polymerization apparatus, carry out the copolymerization of ethene and 1-hexene second with stagnation pressure 2.0MPaG, 70 ℃ of polymerization temperatures, linear gas velocity 0.7m/.
The limit is 4.1g/hr, is that the ratio of 5 mMs/hr is supplied with continuously with TIBA that with the pre-polymerized catalyst (2) of above-mentioned preparation the limit begins polymerization.In order between polymerization period, to keep certain gas composition, supply with ethene, 1-hexene, hydrogen, nitrogen (gas composition (mol ratio) continuously; 1-hexene/ethene=0.04, hydrogen/ethene=4.0 * 10
-4, ethylene concentration=71%).
The receipts amount of resulting ethene-1-hexene copolymer is 6.0kg/hr, and DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 98 ℃, and the density that records with the density gradient column method is 0.903g/cm
3, MFR (ASTM-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute, Mw/Mn (molecular weight distribution) is 2.6.
Wherein, also resulting ethene-1-hexene copolymer is designated as ethene-alpha-olefin copolymer (B-1).
[manufacturing of ethene-alpha-olefin copolymer (B-2)]
In the manufacturing of ethene-alpha-olefin copolymer (B-1), polymerization temperature is changed to 80 ℃, gas composition (mol ratio) is changed to 1-hexene/ethene=0.03, hydrogen/ethene=4.2 * 10
-4, ethylene concentration=71%, in addition, operate equally with the manufacturing of ethene-alpha-olefin copolymer (B-1), obtain ethene-1-hexene copolymer.
The receipts amount of resulting ethene-1-hexene copolymer is 6.0kg/hr, and DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 113 ℃, and the density that records with the density gradient column method is 0.913g/cm
3, MFR (ASTM-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute, Mw/Mn (molecular weight distribution) is 2.6.
Wherein, also resulting ethene-1-hexene copolymer is designated as ethene-alpha-olefin copolymer (B-2).
[manufacturing of ethene-alpha-olefin copolymer (B-3)]
In the manufacturing of ethene-alpha-olefin copolymer (B-1), polymerization temperature is changed to 80 ℃, gas composition (mol ratio) is changed to 1-hexene/ethene=0.02, hydrogen/ethene=4.6 * 10
-4, ethylene concentration=70%, in addition, operate equally with the manufacturing of ethene-alpha-olefin copolymer (B-1), obtain ethene-1-hexene copolymer.
The receipts amount of resulting ethene-1-hexene copolymer is 5.8kg/hr, and DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 120 ℃, and the density that records with the density gradient column method is 0.924g/cm
3, MFR (ASTM-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute, Mw/Mn (molecular weight distribution) is 2.6.
Wherein, also resulting ethene-1-hexene copolymer is designated as ethene-alpha-olefin copolymer (B-3).
[embodiment A 1]
With propylene resin (A-1) 97 weight portions and ethene-alpha-olefin copolymer (B-1) 3 weight portions, also have ADK STAB NA-21 (ADEKA corporate system: contain two (2 as nucleator (D); 4; 8; 10-tetra-tert-6-hydroxyl-12H-dibenzo [d; G] [1,3,2] dioxy phospha eight ring-6-oxides) aluminium hydroxide salt is as the aromatic phosphonic acid ester compound class nucleator of main component) 0.15 weight portion and as the phenol anti-oxidant of additive [[3-(3 for pentaerythrite four; The 5-di-tert-butyl-hydroxy phenyl) propionic ester]] 0.10 weight portion, Phosphorus anti-oxidant [three (2; The 4-di-tert-butyl-phenyl) phosphite ester] 0.10 weight portion, as calcium stearate 0.09 weight portion of nertralizer, mix with Henschel mixer as glyceryl monostearate 0.10 weight portion of antistatic additive, use the double screw extruder (NR-36) of the Nakatani of Co., Ltd. machinery system under following condition, to carry out melting mixing in this mixture, obtain the line material.
(double screw extruder condition)
Model: NR-36
Screw speed 250rpm
200 ℃ of resin temperatures
With resulting line material water-cooled but after, cut off with comminutor, obtain the pellet of olefin polymer compositions (E-1) thus.
The melt flow rate (MFR) (MFR) of olefin polymer compositions (E-1) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 7.0g/10 minute, and DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result of result and hypocrystalline time, foul smell together is illustrated in the table.
Then, use this pellet to implement blow molding.
Use 3 kind of 3 direct blow molding machine of layer multi-layer (PLACO of Co., Ltd. system, 3B504040 blow molding machine), as condition of molding, barrel temperature is set at 200 ℃, and the pressure that is blown into of fluid is set at 5.0kg/cm
2Utilize the molten parison of the crosshead mold forming of mold hole dimension 14.0mm, core size 12.5mm, make the cylindric multilayered blow container of 2 layers of structure of weight 34g, inner capacities 780ml, oral area major diameter of thread 27.0mm, body week external diameter 72mm, body week average wall thickness 0.5mmt for external diameter 20.0mm tubular.
Particularly; Do not use the extruder of internal layer; And use barrel temperature to be set at 200 ℃ intermediate layer and outer field extruder, will be used for base material (internal layer) propylene random copolymers B251VT (Puriman Polymer Co., Ltd's system, melt flow rate (MFR) (MFR) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 1.2g/10 minute; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 146 ℃) with the extruder in intermediate layer, with olefin polymer compositions (E-1) with outer field extruder, so that outer wall thickness rate example is 15% mode fusion; After being the molten parison of tubular through the crosshead mold forming; Temperature being adjusted into 25 ℃ blow mold clamping, make its stretching be attached to mould and cooling curing obtains multilayered blow container with compressed air through water-flow circuit.Wherein,, use the mould and these the two kinds of moulds of mould that carried out blasting treatment #200 that have carried out blasting treatment #400 as surface treatment, use each mould to obtain multilayered blow container as blow mold.
Use resulting multilayered blow container to use bottle, measure turbidity, gloss (gloss), mouldability, cementability, resistance to impact (full water falls impact strength), being clamminess property through the evaluation method of following record as test.In addition, whether influential for the surface treatment of studying mould to the gloss of the multilayered blow container that obtains, use two kinds of Mold Making multilayered blow containers, estimate its gloss respectively.These results of expression in table.
[embodiment A 2]
Except the ratio that changes to propylene resin (A-1) 95.5 weight portions and ethene-alpha-olefin copolymer (B-1) 4.5 weight portions, carry out equally with embodiment A 1.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the embodiment A 2 (E-2) (ASTMD-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
[embodiment A 3]
During multi-layer blow molding; Replace being used for the propylene random copolymers B251VT (Puriman Polymer Co., Ltd's system) of base material (internal layer); Use propylene random block copolymer B 511QA (Puriman Polymer Co., Ltd's system, melt flow rate (MFR) (MFR) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) are 1.2g/10 minute in the intermediate layer; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 158 ℃), in addition, carry out equally with embodiment A 2.
Ecbatic in table.
[embodiment A 4]
During multi-layer blow molding; Replace being used for the propylene random copolymers B251VT (Puriman Polymer Co., Ltd's system) of base material (internal layer); Use PE resinoid HDPE, HZ-6008B (Puriman Polymer Co., Ltd's system in the intermediate layer; Melt flow rate (MFR) (MFR) (ASTMD-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 0.7g/10 minute, and the density that records with the density gradient column method is 0.958g/cm
3), in addition, carry out equally with embodiment A 2.
Ecbatic in table.
[embodiment A 5]
Except the ratio that changes to propylene resin (A-1) 80.0 weight portions and ethene-alpha-olefin copolymer (B-1) 20.0 weight portions, carry out equally with embodiment A 1.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the embodiment A 5 (E-3) (ASTMD-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 148 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
[embodiment A 6]
As nucleator (D), replace ADK STAB NA-21 (ADEKA corporate system) 0.15 weight portion, change to Gel All MD (New Japan Chem Co., Ltd's goods name; Chemical name=1,3,2; 4-two (to the methyl benzal) D-sorbite; Be recited as G-MD in the table) 0.30 weight portion, in addition, carry out with embodiment A 2 equally.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the embodiment A 6 (E-7) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 149 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
[embodiment A 7]
Propylene resin (A-1) is replaced with propylene resin (A-4), when mixing, add [2 as organic peroxide with Henschel mixer; 5-dimethyl-2; 5-two (benzoyl peroxide) hexane] 0.006 weight portion, in addition, carry out with embodiment A 2 equally.
The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the embodiment A 7 (E-20) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
[Comparative examples A 1]
Except the ratio that changes to propylene resin (A-1) 100 weight portions and ethene-alpha-olefin copolymer (B-1) 0 weight portion, carry out equally with embodiment A 1.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 1 (E-4) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 1, owing to do not cooperate ethene-alpha-olefin copolymer (B), so the condition of discontented unabridged version claim.Owing to do not cooperate ethene-alpha-olefin copolymer (B), so cementability and resistance to impact (full water falls impact strength) are poor.
[Comparative examples A 2]
Except the ratio that changes to propylene resin (A-1) 70.0 weight portions and ethene-alpha-olefin copolymer (B-1) 30.0 weight portions, carry out equally with embodiment A 1.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 2 (E-5) (ASTMD-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 2, the use level of ethene-alpha-olefin copolymer (B) is higher than the scope of stipulating in the claim.Therefore being clamminess property is poor.
[Comparative examples A 3]
Except not adding ADK STAB NA-21 (ADEKA corporate system), carry out equally with embodiment A 2 as nucleator (D).The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 3 (E-6) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 145 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 3, owing to do not cooperate nucleator (D), so the condition of discontented unabridged version claim 1.Therefore gloss (gloss) is poor.
[Comparative examples A 4]
Change to the propylene resin (A-2) except replacing propylene resin (A-1), carry out equally with embodiment A 2.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 4 (E-8) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 138 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 4, the DSC fusing point of propylene resin (A) (according to JIS-K7121, the crystalline melting point that records with DSC) is lower than the scope of claim defined.Therefore mouldability is poor with being clamminess property.
[Comparative examples A 5]
Change to the propylene resin (A-3) except replacing propylene resin (A-1), carry out equally with embodiment A 2.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 5 (E-9) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 158 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 5, the DSC fusing point of propylene resin (A) (according to JIS-K7121, the crystalline melting point that records with DSC) is higher than the scope of claim defined.Therefore resistance to impact (full water falls impact strength) is poor.
[Comparative examples A 6]
Change to the propylene resin (A-4) except replacing propylene resin (A-1), carry out equally with embodiment A 2.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 6 (E-10) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 3.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 6, the melt flow rate (MFR) (MFR) of olefin polymer compositions (E) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is lower than the scope of claim defined.Therefore gloss (gloss) is poor.
[Comparative examples A 7]
Change to the propylene resin (A-5) except replacing propylene resin (A-1), carry out equally with embodiment A 2.The melt flow rate (MFR) (MFR) of resulting olefin polymer compositions (E-11) in the Comparative examples A 7 (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 15.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 7, the melt flow rate (MFR) (MFR) of olefin polymer compositions (E) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is higher than the scope of claim defined.Therefore mouldability and resistance to impact (full water falls impact strength) are poor.
[Comparative examples A 8]
Change to the ethene-alpha-olefin copolymer (B-2) except replacing ethene-alpha-olefin copolymer (B-1), carry out equally with embodiment A 2.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 8 (E-12) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
Comparative examples A 8 employed ethene-alpha-olefin copolymers (B-2), the DSC fusing point of ethene-alpha-olefin copolymer (B) (according to JIS-K7121, the crystalline melting point that records with DSC) is higher than the scope of claim defined.Therefore cementability and resistance to impact (full water falls impact strength) are poor.And the resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 9]
Except the ratio that changes to propylene resin (A-1) 90.0 weight portions and ethene-alpha-olefin copolymer (B-2) 10.0 weight portions, carry out equally with Comparative examples A 8.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 9 (E-13) (ASTMD-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
The ethene-alpha-olefin copolymer (B-2) that uses in the Comparative examples A 9, the DSC fusing point of ethene-alpha-olefin copolymer (B) (according to JIS-K7121, the crystalline melting point that records with DSC) is higher than the scope of claim defined.Therefore cementability and resistance to impact (full water falls impact strength) are poor.And the resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 10]
Except the ratio that changes to propylene resin (A-1) 80.0 weight portions and ethene-alpha-olefin copolymer (B-2) 20.0 weight portions, carry out equally with Comparative examples A 8.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 10 (E-14) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
The ethene-alpha-olefin copolymer (B-2) that uses in the Comparative examples A 10, the DSC fusing point of ethene-alpha-olefin copolymer (B) (according to JIS-K7121, the crystalline melting point that records with DSC) is higher than the scope of claim defined.Therefore cementability and resistance to impact (full water falls impact strength) are poor.And the resistance to impact and the balanced bad of characteristic of being clamminess.
[Comparative examples A 11]
Change to the ethene-alpha-olefin copolymer (B-3) except replacing ethene-alpha-olefin copolymer (B-1), carry out equally with embodiment A 2.The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 11 (E-15) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
The ethene-alpha-olefin copolymer (B-3) that uses in the Comparative examples A 11, the DSC fusing point of ethene-alpha-olefin copolymer (B) (according to JIS-K7121, the crystalline melting point that records with DSC) is higher than the scope of claim defined.Therefore gloss (gloss), cementability and resistance to impact (full water falls impact strength) are poor.And the resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 12]
Replace ethene-alpha-olefin copolymer (B-1); Change to not with metallocene catalyst with PE resinoid L-LDPE (straight chain shape low density polyethylene (LDPE)), ULT-ZEX 1030L (Puriman Polymer Co., Ltd's system, the density 0.909g/cm of Ziegler-Natta catalyst manufacturing
3Melt flow rate (MFR) (MFR) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 7.0g/10min, and DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 115 ℃); In addition, carry out equally with embodiment A 2.
The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 12 (E-16) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 12, replace ethene-alpha-olefin copolymer (B), use ULT-ZEX1030L.The DSC fusing point of ULT-ZEX 1030L (according to JIS-K7121, the crystalline melting point that records with DSC) is 115 ℃, is higher than the scope of DSC fusing point of the ethene-alpha-olefin copolymer (B) of claim defined.And ULT-ZEX 1030L not with metallocene catalyst with the Ziegler-Natta catalyst polymerization, cementability, being clamminess property and the resistance to impact (full water falls impact strength) of the multilayered blow container that is therefore formed by olefin polymer compositions (E-16) are poor.And the resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 13]
Replace ethene-alpha-olefin copolymer (B-1), change to PE resinoid HDPE (high density polyethylene (HDPE)), HZ-2100J (Puriman Polymer Co., Ltd's system, density 0.956g/cm
3Melt flow rate (MFR) (MFR) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 11.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is that 131 ℃, Mw/Mn (molecular weight distribution) are 7.0), change to the ratio of propylene resin (A-1) 90.0 weight portions and PE resinoid HDPE, HZ-2100J (Puriman Polymer Co., Ltd's system) 10.0 weight portions; In addition, carry out equally with embodiment A 1.
The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 13 (E-17) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 8.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 13, use HZ-2100J to replace ethene-alpha-olefin copolymer (B).The DSC fusing point of HZ-2100J (according to JIS-K7121, the crystalline melting point that records with DSC) is 131 ℃, is higher than the scope of DSC fusing point of the ethene-alpha-olefin copolymer (B) of claim defined.And the density that HZ-2100J records with the density gradient column method is 0.956g/cm
3The cementability and the resistance to impact (full water falls impact strength) of the multilayered blow container that is therefore formed by olefin polymer compositions (E-17) are poor.And the resistance to impact and the characteristic that is clamminess is balanced bad.
[Comparative examples A 14]
Replace ethene-alpha-olefin copolymer (B-1),, change to TAFMER P-0680 (polyethylene rubber (EPR), Mitsui Chemicals, Inc's system, density 0.870g/cm as ethene-alpha-olefin copolymer (B)
3, melt flow rate (MFR) (MFR) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) be 1.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) detection less than.), change to propylene resin (A-1) 90.0 weight portions and, in addition, carry out equally with embodiment A 1 as the ratio of TAFMER P-0680 (Mitsui Chemicals, Inc's system) 10.0 weight portions of ethene-alpha-olefin copolymer (B).
The melt flow rate (MFR) (MFR) of the olefin polymer compositions that obtains in the Comparative examples A 14 (E-18) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 6.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 14, use TAFMER P-0680 (Mitsui Chemicals, Inc's system) to replace ethene-alpha-olefin copolymer (B).TAFMER P-0680 detects less than DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC), and (B) is unsuitable with ethene-alpha-olefin copolymer.In addition, melt flow rate (MFR) (MFR) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 1.0g/10 minute, and the density that records with the density gradient column method also is 0.870g/cm
3
Glossiness (gloss), cementability and the being clamminess property of the multilayered blow container that therefore, is formed by olefin polymer compositions (E-18) are poor.
[Comparative examples A 15]
Replace ethene-alpha-olefin copolymer (B-1), change to TAFMER P-0180 (polyethylene rubber (EPR), Mitsui Chemicals, Inc's system, density 0.870g/cm as ethene-alpha-olefin copolymer (B)
3, melt flow rate (MFR) (MFR) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) be 8.0g/10 minute, DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) detection less than.), change to propylene resin (A-1) 90.0 weight portions and, in addition, carry out equally with embodiment A 1 as the ratio of TAFMER P-0180 (Mitsui Chemicals, Inc's system) 10.0 weight portions of ethene-alpha-olefin copolymer (B).
The melt flow rate (MFR) (MFR) of Comparative examples A 15 resulting olefin polymer compositions (E-19) (ASTM D-1238,230 ℃ of temperature of mensuration, load 2.16kg) is 7.0g/10 minute; DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result and the multilayered blow container result of the test of result and hypocrystalline time, foul smell together are illustrated in the table.
In Comparative examples A 15, replace ethene-alpha-olefin copolymer (B), use TAFMERP-0180 (Mitsui Chemicals, Inc's system).TAFMER P-0180 detects less than DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC), and (B) is unsuitable with ethene-alpha-olefin copolymer.In addition, density is 0.870g/cm
3The cementability of the multilayered blow container that therefore, is formed by olefin polymer compositions (E-19) is poor with being clamminess property.
[Embodiment B 1]
With propylene resin (A-1) 97 weight portions and ethene-alpha-olefin copolymer (B-1) 3 weight portions, also have ADK STAB NA-21 (ADEKA corporate system: contain two (2 as nucleator (D); 4; 8; 10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3; 2] dioxy phospha eight ring-6-oxides) aluminium hydroxide salt is the aromatic phosphonic acid ester compound class nucleator of main component) 0.15 weight portion, as the TAFMER P-0280 of the Mitsui Chemicals society system of low density ethylene-alpha olefin copolymer (F) (ethylene-propylene copolymer, the density that records with the density gradient column method: 0.870g/cm
3, Ziegler-Natta catalyst, DSC fusing point be (according to JIS-K7121; The crystalline melting point that records with DSC): do not observe; MFR (ASTM-1238, measure 230 ℃ of temperature, load 2.16kg): 5.4g/10 minute) 15 weight portions and as the phenol anti-oxidant of additive [[3-(3 for pentaerythrite four; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.10 weight portion, Phosphorus anti-oxidant [three (2; The 4-di-tert-butyl-phenyl) phosphite ester]] 0.10 weight portion, as calcium stearate 0.09 weight portion of nertralizer; Mix with Henschel mixer, use double screw extruder (NR-36) melting mixing under following condition of the Nakatani of Co., Ltd. machinery system to obtain the line material in this mixture.
(double screw extruder condition)
Model: NR-36
Screw speed 250rpm
200 ℃ of resin temperatures
With resulting line material water-cooled but after, cut off with comminutor, obtain the pellet of olefin polymer compositions (E-21) thus.
The melt flow rate (MFR) (MFR) of Propenes resin composition (E-21) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 7.0g/10 minute, and DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC) is 147 ℃.
The mensuration result of result and hypocrystalline time, foul smell together is illustrated in the table.
Then, use this pellet to implement blow molding.
Use 3 kind of 3 direct blow molding machine of layer multi-layer (PLACO of Co., Ltd. system, 3B504040 blow molding machine), as condition of molding, barrel temperature is set at 200 ℃, and the pressure that is blown into of fluid is set at 5.0kg/cm
2Crosshead mold forming through mold hole dimension 14.0mm, core size 12.5mm is the molten parison of external diameter 20.0mm tubular, makes the cylindric multilayered blow container of 2 layers of structure of weight 34g, inner capacities 780ml, oral area major diameter of thread 27.0mm, body week external diameter 72mm, body week average wall thickness 0.5mmt.
Particularly; Do not use the extruder of internal layer; And use barrel temperature is set at 200 ℃ intermediate layer and outer field extruder, will be used for base material (internal layer) propylene random copolymers B251VT (Puriman Polymer Co., Ltd's system, melt flow rate (MFR) (MFR) (ASTM D-1238, measure 230 ℃ of temperature, load 2.16kg) is 1.2g/10 minute; The DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC) be 146 ℃) with the extruder in intermediate layer, with olefin polymer compositions (E-21) with outer field extruder, so that outer wall thickness rate example is 15% mode fusion; After utilizing the molten parison of crosshead mold forming for tubular; Temperature being adjusted into 25 ℃ blow mold clamping, make its stretching be attached to mould and cooling curing obtains multilayered blow container with compressed air through water-flow circuit.Wherein,, use the mould and these the two kinds of moulds of mould that carried out blasting treatment #200 that have carried out blasting treatment #400 as surface treatment, use each mould to obtain multilayered blow container as blow mold.
Use resulting multilayered blow container as test with bottle, the evaluation method through following record is measured turbidity, gloss (gloss), mouldability, cementability, is clamminess, resistance to impact (full water falls impact strength) and low temperature resistance to impact (full water falls impact strength).In addition, whether influential for the surface treatment of studying mould to the gloss of the multilayered blow container that obtains, use two kinds of Mold Making multilayered blow containers, estimate its gloss respectively.These results of expression in table.
[Embodiment B 2]
Low density ethylene-alpha olefin copolymer (F) is changed to TAFMER A-4085S (ethylene-butene copolymer, the density that records with the density gradient column method: 0.885g/cm of Mitsui Chemicals society system from the TAFMER P-0280 of Mitsui Chemicals society system
3, the DSC fusing point is (according to JIS-K7121; The crystalline melting point that records with DSC): 70 ℃, MFR (ASTM-1238, measure 230 ℃ of temperature, load 2.16kg): 6.7g/10 minute); Its use level is changed to 7 weight portions from 15 weight portions, use glyceryl monostearate 0.1 weight portion as antistatic additive, in addition; Carry out equally with Embodiment B 1, obtain the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[Embodiment B 3]
(A-1) changes to 90 weight portions with propylene resin; (B-1) changes to 10 weight portions with ethene-alpha-olefin copolymer; Low density ethylene-alpha olefin copolymer (F) from the TAFMERA-4085S that the TAFMER P-0280 of Mitsui Chemicals society system changes to Mitsui Chemicals society system, is changed to 5 weight portions with its use level from 15 weight portions, in addition; Carry out equally with Embodiment B 1, obtain the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[Embodiment B 4]
Except the TAFMER P-0280 of low density ethylene-alpha olefin copolymer (F) from Mitsui Chemicals society system changed to the TAFMER A-4085S of Mitsui Chemicals society system, carry out equally with Embodiment B 1, obtain the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[Embodiment B 5]
Except not using low density ethylene-alpha olefin copolymer (F), carry out equally with Embodiment B 1, obtain the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[Embodiment B 6]
(A-1) changes to 95.5 weight portions with propylene resin; (B-1) changes to 4.5 weight portions with ethene-alpha-olefin copolymer; Do not use low density ethylene-alpha olefin copolymer (F), use glyceryl monostearate 0.1 weight portion as antistatic additive, in addition; Carry out equally with Embodiment B 1, obtain the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[Embodiment B 7]
(A-1) changes to 90 weight portions with propylene resin, and (B-1) changes to 10 weight portions with ethene-alpha-olefin copolymer, do not use low density ethylene-alpha olefin copolymer (F), in addition, carries out equally with Embodiment B 1, obtains the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[reference example B1]
(A-1) changes to 95.5 weight portions with propylene resin; (B-1) changes to 4.5 weight portions with ethene-alpha-olefin copolymer, and (F) changes to 25 weight portions from 15 weight portions with low density ethylene-alpha olefin copolymer, in addition; Carry out equally with Embodiment B 1, obtain the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[comparative example B1]
Ethene-alpha-olefin copolymer (B-1) is changed to ethene-alpha-olefin copolymer (B-2); (A-1) changes to 95.5 weight portions with propylene resin; Use ethene-alpha-olefin copolymer (B-2) 4.5 weight portions; Low density ethylene-alpha olefin copolymer (F) is changed to TAFMER P-0275 (ethylene-propylene copolymer, the density that records with the density gradient column method: 0.860g/cm of Mitsui Chemicals society system from the TAFMER P-0280 of Mitsui Chemicals society system
3, DSC fusing point (according to JIS-K7121, the crystalline melting point that records with DSC): do not observe MFR (ASTM-1238, measure 230 ℃ of temperature, load 2.16kg): 5.4g/10 minute), in addition, carry out equally with Embodiment B 1, obtain the line material.
Except using this line material, carry out equally with Embodiment B 1, obtain multilayered blow container.
Ecbatic in table.
[evaluation method]
According to the method for following record, measure the rerum natura of acronal (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) or olefin polymer compositions (E).Ecbatic in table.
[MFR (melt flow rate (MFR))]
The MFR of aforesaid propylene resinoid (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and olefin polymer compositions (E) is according to ASTM D-1238, to measure 230 ℃ of temperature, load 2.16kg mensuration.
The line material that collection obtains during according to ASTM D-1238 instrumentation MFR uses in the mensuration of following density.
[fusing point (Tm)]
The crystalline melting point of aforesaid propylene resinoid (A), ethene-alpha-olefin copolymer (B), low density ethylene-alpha olefin copolymer (F) and olefin polymer compositions (E) is according to JIS-K7121; Use differential scanning calorimetry (DSC) (DSC, PerkinElmer corporate system (Diamond DSC)) to measure.Wherein will be defined as crystalline melting point (Tm) on the summit of the endothermic peak in the 3rd step of measuring.Endothermic peak has when a plurality of, and the endothermic peak summit that peak height is maximum is defined as crystalline melting point (Tm).
(condition determination)
Measure environment: nitrogen atmosphere
Sample size: 5mg
Sample shape: press mold (230 ℃ of moulding, thickness 200～400 μ m)
The 1st step: be warming up to 240 ℃ from 30 ℃ with 10 ℃/min, keep 10min.
The 2nd step: be cooled to 60 ℃ with 10 ℃/min.
The 3rd step: be warming up to 240 ℃ with 10 ℃/min.
[hypocrystalline time (T
1/2)]
Hypocrystalline time (the T of olefin polymer compositions (E)
1/2) use differential scanning calorimetry (DSC) (DSC, PerkinElmer corporate system (DSC7)) to measure.Under 125 ℃ of isothermys, make olefin polymer compositions (E) crystallization; Measure the thermal discharge of accompanying crystallizationization this moment, measure and begin (crystallization begins) from heat release and reach time (second) till half the value of total thermal discharge to thermal discharge as hypocrystalline time (t
1/2).Hypocrystalline time (t
1/2) the more for a short time crystallization speed that means of value big more.
(condition determination)
Measure environment: nitrogen atmosphere
Sample size: 5mg
Sample shape: press mold (230 ℃ of moulding, thickness 200～400 μ m)
The 1st step: be warming up to 220 ℃ from 30 ℃ with 10 ℃/min, keep 3min.
The 2nd step: be cooled to 125 ℃ with 60 ℃/min.
[density]
Density for ethene-alpha-olefin copolymer (B) and low density ethylene-alpha olefin copolymer (F); The ethene-alpha-olefin copolymer (B) that obtains during with the mensuration of above-mentioned MFR and the line material of low density ethylene-alpha olefin copolymer (F) are respectively 120 ℃ of heat treatments 1 hour; After slowly cooling to room temperature through 1 hour, measure with density gradient column.
[Mw/Mn (molecular weight distribution)]
The Mw/Mn of aforesaid propylene resinoid (A) and ethene-alpha-olefin copolymer (B) tries to achieve through the weight average molecular weight (Mw) and the number-average molecular weight (Mn) that record with following determination method.
Mw and Mn use the following time-and-motion study of Waters corporate system GPC-150C Plus.
Splitter uses TSKgel GMH6-HT and TSKgel GMH6-HTL; Column dimension is respectively internal diameter 7.5mm, length 600mm, and column temperature is made as 140 ℃, and flowing phase is used o-dichlorohenzene (with the pure pharmaceutical worker's industry of light (strain)) and as BHT (with the pure pharmaceutical worker's industry of light (strain)) the 0.025 weight % of anti-oxidant; Flowed with 1.0ml/ minute; Sample solution concentration is made as 0.1 weight %, and sample size is made as 500 microlitres, uses the differential refractometer as detector.
For polystyrene standard, molecular weight is in Mw＜1000 and Mw＞4 * 10
6The time use the polystyrene standard of eastern Cao (strain) system, molecular weight is in 1000≤Mw≤4 * 10
6The time use the polystyrene standard of Pressure Chemical corporate system.
[turbidity]
For the turbidity of multilayered blow container, downcut location from the container main part, be benchmark with JIS-K7105, use nephelometer (NIPPON DENSHOKU (NDH2000)) to measure turbidity (mist value).The value of turbidity is more little, we can say that the transparency is more excellent.
[gloss]
The evaluation of glossiness is estimated through the mensuration of following gloss (gloss).For the gloss (gloss) of multilayered blow container, downcut location from the container main part, be benchmark with JIS-K7105, use gloss meter (NIPPON DENSHOKU (VG2000)) to measure outer field 60 degree glossiness.The value of gloss (gloss) is big more, we can say to have excellent glossiness more.
[mouldability]
For the mouldability of multilayered blow container, observe resulting container appearances, estimate with the fold that the molten parison rough surface when container body partly has or not blowing causes.
AA: do not have fold or not obvious fully, good forming ability
BB: can observe fold or obvious, insufficient formability
[cementability]
At the interlayer of the outermost layer that is formed by the application's olefin polymer compositions (E) of multilayered blow container and adjacent layer, that estimates that burr excision portion container top and container bottom pinch off portion take place when container formation layer peels off having or not of observed rope form of the ability that causes or banded bad order.
AA: no bad order, cementability is good
BB: carefully see and can observe bad order, cementability is poor slightly
CC: tangible bad order is arranged, and cementability is poor
[foul smell]
Foul smell for olefin polymer compositions (E); The pellet of 10g said composition is added in the 100ml conical flask, cover the gag sealing, take out after 1 hour with the baking oven heating at 100 ℃; Open gag then immediately, the quality of foul smell takes place as judging with sensory test.
AA---does not have foul smell
BB---has foul smell slightly
CC---has foul smell
[resistance to impact]
The evaluation of resistance to impact has or not through the surface checking that utilizes following full water dropping impact strength determination method to record to be estimated.To in multilayered blow container (inner capacities 780ml), be cooled to 5 ℃ (evaluations of resistance to impact) by the filling containers of fills with water; 10 containers that will respectively be cooled to this temperature respectively vertically fall from the high position of concrete surface 1m from the bottom surface of container, fall standard evaluation according to following.The judgement of breaking was judged with having or not of top layer be full of cracks generation.
AA: all do not have generation of cracks on the surface
BB: more than half do not have generation of cracks on the surface, but at least 1 in surperficial generation of cracks
CC: more than half in surperficial generation of cracks
It is good more that full water falls the evaluation of impact strength determination method, we can say that resistance to impact is good more.
[low temperature resistance to impact]
The evaluation of low temperature resistance to impact has or not through the surface checking that utilizes following full water dropping impact strength determination method to record to be estimated.The filling containers that in multilayered blow container (inner capacities 780ml), fill with the liquid that is made up of glycol/water=5/5 (volume) is cooled to-5 ℃ (evaluations of low temperature resistance to impact); 10 containers that will respectively be cooled to this temperature respectively vertically fall from the high position of 1m of concrete surface from the bottom surface of container, fall standard evaluation according to following.The judgement of breaking was judged with having or not of top layer be full of cracks generation.
AA: all do not have generation of cracks on the surface
BB: more than half do not have generation of cracks on the surface, but at least 1 in surperficial generation of cracks
CC: more than half in surperficial generation of cracks
It is good more that full water falls the evaluation of impact strength determination method, we can say that the low temperature resistance to impact is good more.
[being clamminess property]
About the sense of touch on the surface of multilayered blow container, to after the moulding 48～72 hours on the surface of 23 ℃ of adjusted bottles of states, have or not the quality of the sense of touch that is clamminess as judging with sensory test.
AA: do not feel fully to be clamminess
BB: feel hardly to be clamminess
CC: what are felt is clamminess
DD: feel to be clamminess
In the application's multilayered blow container, the container that preferably is not clamminess, it is poor that the container that is clamminess is evaluated as being clamminess property.
[by
13In the propylene resin that C-NMR calculates from the weight of the construction unit of alpha-olefin]
Will by
13That C-NMR calculates, be that the total of the construction unit of the alkene more than a kind in 4～20 the alpha-olefin is when being made as 100 weight % from the construction unit of propylene with from being selected from ethene and carbon number; From being selected from the weight that ethene and carbon number are the construction unit of the alkene more than a kind in 4～20 the alpha-olefin, according to
13The mensuration of C-NMR is described below and measures, calculates and confirm.
13The C-NMR condition determination
Determinator: the system LA400 of NEC type nuclear magnetic resonance device
Mode determination: BCM (Bilevel Complete decoupling)
Observing frequency: 100.4MHz
Observation scope: 17006.8Hz
45 ° of pulse width: C nuclears (7.8 μ second)
Pulse-recurrence time: 5 seconds
Coupon:
Coupon rotating speed: 12Hz
The tired number of times of calculating: 20000 times
Measure temperature: 125 ℃
Solvent: 1,2,4-trichloro-benzenes: 0.35ml/ heavy benzol: 0.2ml
Sample size: about 40mg
When comonomer is ethene, according to following document (1), by resulting
13C-NMR spectrum is confirmed the distribute ratio of (two unit groups (2 cellular chain) distribution) of monomer chain, calculates in the propylene resin (A) mole fraction (mol%) from the construction unit of ethene (below be designated as E (mol%)) and from the mole fraction (mol%) of the construction unit of propylene (below be designated as P (mol%)).Be scaled weight % from the E (mol%) and the P (mol%) that are tried to achieve, calculate in the propylene resin (A) from the weight % of the construction unit of propylene with from the weight % of the construction unit of ethene.
Document (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Macromolecules 1982,15, (4), 1150-1152
Wherein, in evaluation,, use has been carried out the multilayered blow container of the Mold Making of blasting treatment #400 and measured for turbidity, mouldability, cementability, resistance to impact, low temperature resistance to impact and being clamminess property about the rerum natura of multilayered blow container.
[table 1]
[table 2]
[table 3]
[table 4]
Claims (13)
1. multilayered blow container is characterized in that:
The employed resin of outermost layer comprises olefin polymer compositions (E); This olefin polymer compositions (E) contains propylene resin (A) 80～98 weight portions, ethene-alpha-olefin copolymer (B) 2～20 weight portions and nucleator (D) 0.01～0.5 weight portion; Wherein, (A) and (B) add up to 100 weight portions
Said propylene resin (A) satisfies following condition (A-1) and (A-2),
Said ethene-alpha-olefin copolymer (B) satisfies following condition (B-1) and (B-2),
Said olefin polymer compositions (E) satisfies following condition (E-1),
(A-1) for propylene be selected from the copolymer that ethene and carbon number are the alkene more than a kind in 4～20 the alpha-olefin;
(A-2) according to JIS-K7121, the crystalline melting point that records with differential scanning calorimetry (DSC) (DSC) is 140～155 ℃ a scope;
(B-1) for ethene and the carbon number more than a kind be the copolymer of 4～20 alpha-olefin;
(B-2) according to JIS-K7121, the crystalline melting point that records with DSC is more than 85 ℃ and less than 110 ℃ scope;
(E-1), be 5～10g/10 minute scope to measure melt flow rate (MFR) (MFR) that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.
2. multilayered blow container as claimed in claim 1 is characterized in that:
Said polymerization of olefines compositions (E) also contains low density ethylene-alpha olefin copolymer (F) 0.1～20 weight portion,
Said low density ethylene-alpha olefin copolymer (F) satisfies following condition (F-1) and (F-2),
Density (the d that said ethene-alpha-olefin copolymer (B) records with the density gradient column method
B[g/cm
3]) and the density (d that records with the density gradient column method of low density ethylene-alpha olefin copolymer (F)
F[g/cm
3]) satisfy following condition (X-1),
(F-1) for ethene and the carbon number more than a kind be the copolymer of 3～20 alpha-olefin;
(F-2) according to JIS-K7121, the crystalline melting point that records with DSC is below 89 ℃, or does not observe the peak based on crystalline melting point;
（X－1）d
B[g/cm
3]＞d
F[g/cm
3]，0.010[g/cm
3]≤（d
B－d
F）[g/cm
3]≤0.050[g/cm
3]。
3. multilayered blow container as claimed in claim 1 is characterized in that:
Said ethene-alpha-olefin copolymer (B) also satisfies following condition (B-4),
(B-4) density that records with the density gradient column method is 0.880～0.910g/cm
3Scope.
4. multilayered blow container as claimed in claim 2 is characterized in that:
Said ethene-alpha-olefin copolymer (B) also satisfies following condition (B-4a), and said low density ethylene-alpha olefin copolymer (F) also satisfies following condition (F-3),
(B-4a) density (d that records with the density gradient column method
B[g/cm
3]) be 0.890～0.910g/cm
3Scope;
(F-3) density (d that records with the density gradient column method
F[g/cm
3]) be 0.865～0.900g/cm
3Scope.
5. like each described multilayered blow container in the claim 1～4, it is characterized in that:
Said propylene resin (A) also satisfies following condition (A-4),
(A-4) Mw/Mn that records through GPC is more than 4.0.
6. like each described multilayered blow container in the claim 1～5, it is characterized in that:
Said propylene resin (A) also satisfies following condition (A-3),
(A-3), be 5～10g/10 minute scope to measure MFR that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.
7. like each described multilayered blow container in the claim 1～6, it is characterized in that:
Said ethene-alpha-olefin copolymer (B) also satisfies following condition (B-5),
(B-5) Mw/Mn that records through GPC is 1.2～3.0.
8. like each described multilayered blow container in the claim 1～7, it is characterized in that:
Said ethene-alpha-olefin copolymer (B) also satisfies following condition (B-3),
(B-3), be 5～10g/10 minute scope to measure MFR that 230 ℃ of temperature, 2.16kg load record according to ASTM D-1238.
9. like each described multilayered blow container in the claim 1～8, it is characterized in that:
Said nucleator (D) is for being selected from the compound more than a kind in aromatic phosphonic acid ester compound, carboxylic metallic salt nucleator, polymer nucleator, sorbose alcohols nucleator and the inorganic compound nucleator.
10. like each described multilayered blow container in the claim 1～9, it is characterized in that:
Said propylene resin (A) is 95.5～98 weight portions, and said ethene-alpha-olefin copolymer (B) is 2～4.5 weight portions, wherein, (A) with (B) add up to 100 weight portions.
11. like each described multilayered blow container in the claim 1～10, it is characterized in that: said multilayered blow container has at least one internal layer, this internal layer is formed by acronal (G) or polyvinyls (H).
12. like each described multilayered blow container in the claim 1～11, it is characterized in that: said multilayered blow container obtains through direct blow molding method or the moulding of injection stretch blow molding method.
13. the manufacturing approach of a multilayered blow container is characterized in that:
Use each described olefin polymer compositions (E) and olefin polymer compositions (E) thermoplastic resin composition in addition in the claim 1～9,
Form outermost layer with said olefin polymer compositions (E), said olefin polymer compositions (E) thermoplastic resin composition in addition forms the mode of at least one internal layer, through direct blow molding method or the moulding of injection stretch blow molding method.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-012354 | 2010-01-22 | ||
| JP2010012354 | 2010-01-22 | ||
| JP2010-031430 | 2010-02-16 | ||
| JP2010031430 | 2010-02-16 | ||
| PCT/JP2011/050939 WO2011090101A1 (en) | 2010-01-22 | 2011-01-20 | Multilayer blow-molded container, and process for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102712186A true CN102712186A (en) | 2012-10-03 |
| CN102712186B CN102712186B (en) | 2014-07-16 |
Family
ID=44306901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180006278.4A Active CN102712186B (en) | 2010-01-22 | 2011-01-20 | Multilayer blow-molded container, and process for production thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5379247B2 (en) |
| KR (1) | KR101333450B1 (en) |
| CN (1) | CN102712186B (en) |
| WO (1) | WO2011090101A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014154130A1 (en) * | 2013-03-28 | 2014-10-02 | 优泊公司 | In-mould label and labeled plastic container using same |
| CN106103576A (en) * | 2014-03-10 | 2016-11-09 | 普瑞曼聚合物株式会社 | Propylene resin composition and the stretched container being formed by it |
| CN107107596A (en) * | 2015-01-16 | 2017-08-29 | 普瑞曼聚合物株式会社 | Laminated body, container and its manufacture method and laminated body raw material sheet material |
| CN109689516A (en) * | 2016-09-29 | 2019-04-26 | 陶氏环球技术有限责任公司 | Flexible container with Pop-up spout |
| CN112639011A (en) * | 2018-09-26 | 2021-04-09 | 博里利斯股份公司 | Propylene copolymer compositions having excellent optical and mechanical properties |
| CN115803382A (en) * | 2020-06-30 | 2023-03-14 | 弗纳技术股份有限公司 | Transparent polypropylene composition for thermoforming |
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| JP7055598B2 (en) * | 2017-05-31 | 2022-04-18 | 株式会社プライムポリマー | Sterilization container |
| JP6980452B2 (en) * | 2017-08-09 | 2021-12-15 | 住友化学株式会社 | Hollow container and its manufacturing method, and polypropylene resin composition for blow fill seal |
| JP6935748B2 (en) * | 2018-01-09 | 2021-09-15 | 日本ポリプロ株式会社 | Propylene resin composition and its molded product |
| JP6995184B2 (en) * | 2018-03-20 | 2022-01-14 | 株式会社プライムポリマー | Laminates and liquid packaging bags |
| KR102157673B1 (en) * | 2020-04-28 | 2020-09-21 | 라니홀딩스(주) | Container for food packaging |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263899A (en) * | 1999-02-04 | 2000-08-23 | 株式会社宏大化纤 | Polypropylene block copolymer resin and preparation method thereof |
| CN101384627A (en) * | 2006-02-15 | 2009-03-11 | 三井化学株式会社 | Ethylene resin and blow-molded article comprising the same |
| CN101511930A (en) * | 2006-09-12 | 2009-08-19 | 三井化学株式会社 | Polypropylene resin and blown container |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0631796A (en) * | 1992-07-14 | 1994-02-08 | Chisso Corp | Polyolefin resin-made hollow container |
| JPH09166476A (en) * | 1995-12-13 | 1997-06-24 | Kyoto Puratetsuku:Kk | Liquid-level sensor |
| JPH09165476A (en) * | 1995-12-15 | 1997-06-24 | Chisso Corp | Multilayer hollow vessel |
| JP2009013333A (en) | 2007-07-06 | 2009-01-22 | Sumitomo Chemical Co Ltd | Polypropylene-based resin composition |
-
2011
- 2011-01-20 WO PCT/JP2011/050939 patent/WO2011090101A1/en active Application Filing
- 2011-01-20 JP JP2011550944A patent/JP5379247B2/en active Active
- 2011-01-20 KR KR1020127021432A patent/KR101333450B1/en active IP Right Grant
- 2011-01-20 CN CN201180006278.4A patent/CN102712186B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263899A (en) * | 1999-02-04 | 2000-08-23 | 株式会社宏大化纤 | Polypropylene block copolymer resin and preparation method thereof |
| CN101384627A (en) * | 2006-02-15 | 2009-03-11 | 三井化学株式会社 | Ethylene resin and blow-molded article comprising the same |
| CN101511930A (en) * | 2006-09-12 | 2009-08-19 | 三井化学株式会社 | Polypropylene resin and blown container |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014154130A1 (en) * | 2013-03-28 | 2014-10-02 | 优泊公司 | In-mould label and labeled plastic container using same |
| CN104981857A (en) * | 2013-03-28 | 2015-10-14 | 优泊公司 | In-mould label and labeled plastic container using same |
| CN106103576A (en) * | 2014-03-10 | 2016-11-09 | 普瑞曼聚合物株式会社 | Propylene resin composition and the stretched container being formed by it |
| CN107107596A (en) * | 2015-01-16 | 2017-08-29 | 普瑞曼聚合物株式会社 | Laminated body, container and its manufacture method and laminated body raw material sheet material |
| CN109689516A (en) * | 2016-09-29 | 2019-04-26 | 陶氏环球技术有限责任公司 | Flexible container with Pop-up spout |
| CN112639011A (en) * | 2018-09-26 | 2021-04-09 | 博里利斯股份公司 | Propylene copolymer compositions having excellent optical and mechanical properties |
| CN115803382A (en) * | 2020-06-30 | 2023-03-14 | 弗纳技术股份有限公司 | Transparent polypropylene composition for thermoforming |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011090101A1 (en) | 2013-05-23 |
| JP5379247B2 (en) | 2013-12-25 |
| WO2011090101A1 (en) | 2011-07-28 |
| KR20120104436A (en) | 2012-09-20 |
| KR101333450B1 (en) | 2013-11-26 |
| CN102712186B (en) | 2014-07-16 |
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